Name: 621-84-1|Benzyl carbamate|98%
Brand: Ambeed
SKU: A148795
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1
[ 5753-96-8 ]
[ 621-84-1 ]
[ 77327-87-8 ]

Reference： [1]Bulletin of the Chemical Society of Japan,1980,vol. 53,p. 2905 - 2909

2
[ 95-14-7 ]
[ 621-84-1 ]
[ 298-12-4 ]
[ 124676-19-3 ]

Yield	Reaction Conditions	Operation in experiment
87%	In toluene; at 120℃; for 2h;	To a 250 ml. flask equipped mechanical stirring, was added 2-oxoacetic acid hydrate (9.2 g,0.1 mol), benzyl carbamate (15.1 g, 0.1 mol) and 1H-benzo[dj[1,2,3jtriazole (9.2 g, 0.1 mol), and toluene (300 mL). The resulting solution was stirred for 2 h at 120 C in an oil bath. The resulting mixture was filtered and the solid residue was washed with petroleum ether (3x), and dried in vacuo to give 2-(1H-benzo[dj[1,2,3jtriazol-1-yl)-2-(benzyloxycarbonylamino)aceticacid (28.6 g, 87%) as a white solid that was used without further purification. ESI-MS m/z:327 [M+Hf
87%	In toluene; at 120℃; for 2h;	To a 250 mL flask equipped mechanical stirring, was added 2-oxoacetic acid hydrate (9.2 g, 0.1 mol), benzyl carbamate (15.1 g, 0.1 mol) and 1H-benzo[d][1,2,3]triazole (9.2 g, 0.1 mol), and toluene (300 mL). The resulting solution was stirred for 2 h at 120 C. in an oil bath. The resulting mixture was filtered and the solid residue was washed with petroleum ether (3*), and dried in vacuo to give 2-(1H-benzo[d][1,2,3]triazol-1-yl)-2-(benzyloxycarbonylamino)acetic acid (28.6 g, 87%) as a white solid that was used without further purification. ESI-MS m/z: 327 [M+H]+.
	In toluene; for 18h;Heating / reflux;	[A] mixture of glyoxylic acid monohydrate (4.60g), benzotriazole (5.95g) and benzyl carbamate (7.55g) was heated to reflux in toluene (100ml) for [18H,] under Dean-Stark conditions. The mixture was then allowed to cool to room temperature, and the resulting precipitate collected by filtration. This was then recrystallised from diethyl ether giving an off-white solid [(11.] 66g) [IH] NMR (d6 DMSO, [8)] 5.07 (q+s, 3H) 7.25 (d, 1H) 7.3-7. 63 (m, 6H) 7.92-8. 10 (m, 2H) 9.32 (d, 1H) LC/MS Found ES-= 325 RT= 4. [68MIN]

	In toluene; for 18h;Heating / reflux;	Intermediate 1 Benzotriazol- 1 -yl-benzyloxycarbonylamino-acetic acid A mixture of glyoxylic acid monohydrate (4.6Og), benzotriazole (5.95g) and benzyl carbamate (7.55g) was heated to reflux in toluene (100ml) for 18h, under Dean-Stark conditions. The mixture was then allowed to cool to room temperature, and the resulting precipitate collected by filtration. This was then recrystallised from diethyl ether giving an off-white solid (11.66g)1H NMR (d6 DMSO, delta) 5.07 (q+s, 3H) 7.25 (d, IH) 7.3-7.63 (m,6H) 7.92-8.10 (m, 2H) 9.32 (d, IH)LC/MS Found ES- = 325 RT= 4.68min
134.9 g	In toluene; for 2h;Reflux; Dean-Stark;	A mixture of benzyl carbamate (82.1 g, 0.54 mol), glyoxylic acid monohydrate (50 g, 0.54 mol) and benzotriazole (64.7 g, 0.54 mol) in toluene (2.5 L) was heated at reflux with Dean and Stark water removal for 2 hours. A total of 23 mL of water was collected during the first hour before water evolution ceased. The mixture was allowed to cool to room temperature and the resulting solid filtered and washed with diethyl ether (200 mL). The damp filter cake was dried at 40 C/50 mmHg overnight to give a cream coloured powder (134.9 g).
	In toluene; at 120℃; for 2h;	To a 250 mL flask equipped mechanical stirring, was added 2-oxoacetic acid hydrate (9.2 g, 0.1 mol), benzyl carbamate (15.1 g, 0.1 mol) and 1H-benzo[d][1,2,3]triazole (9.2 g, 0.1 mol), and toluene (300 mL). The resulting solution was stirred for 2 h at 120 oC in an oil bath. The resulting mixture was filtered and the solid residue was washed with petroleum ether (3x), and dried in vacuo to give 2-(1H-benzo[d][1,2,3]triazol-1-yl)-2-(benzyloxycarbonylamino)acetic acid (28.6 g, 87%) as a white solid that was used without further purification. ESI-MS m/z: 327 [M+H]+.

Reference： [1]ACS Medicinal Chemistry Letters,2015,vol. 6,p. 523 - 527
[2]Patent: WO2017/15449,2017,A1 .Location in patent: Page/Page column 51
[3]Patent: US2018/193352,2018,A1 .Location in patent: Paragraph 0205; 0206; 0207
[4]Journal of Organic Chemistry,1990,vol. 55,p. 2206 - 2214
[5]Journal of the Chemical Society. Chemical communications,1989,p. 337 - 338
[6]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 6389 - 6392
[7]Journal of Medicinal Chemistry,2006,vol. 49,p. 2311 - 2319
[8]Patent: WO2004/26843,2004,A1 .Location in patent: Page 54
[9]Patent: WO2007/34127,2007,A1 .Location in patent: Page/Page column 27
[10]Patent: WO2016/20698,2016,A1 .Location in patent: Page/Page column 40; 45
[11]Patent: WO2019/67864,2019,A1 .Location in patent: Page/Page column 63

3
[ 101-02-0 ]
[ 3598-60-5 ]
[ 621-84-1 ]
[ 149194-43-4 ]

Yield	Reaction Conditions	Operation in experiment
57%	With acetic acid at 90℃; for 2h;
55%	In acetic acid at 80 - 85℃; for 1h;
47%	With acetic acid at 80 - 90℃; for 1h;

With acetic acid Heating;

II 4-(N-phthaloyl)butyraldehyde (10), (prepared from phthalic anhydride (9) and 4-aminobutyraldehyde diethylacetal (8)) was heated with triphenyl phosphite and benzyl carbamate in AcOH to give N-ω-Pth-N-α-Cbz-OrnP(OPh)2 (12). Removal of the phthaloyl group using hydrazine hydrate followed by reaction with N,N′-bis-Boc-S-methylthiourea yielded the arginine derivative (14) which was deprotected at the α-N by catalytic hydrogenolysis using H2-10% Pd/C. The deprotected material (15) was then reacted with succinic anhydride and coupled to Biotin-PEG-Novatag Resin using HATU/DIPEA to give (17).

Reference： [1]Joossens; Van Der Veken; Lambeir; Augustyns; Haemers [Journal of Medicinal Chemistry, 2004, vol. 47, # 10, p. 2411 - 2413]
[2]Hamilton; Walker; Walker [Tetrahedron Letters, 1993, vol. 34, # 17, p. 2847 - 2850]
[3]Jackson, Delwin S.; Fraser, Stephanie A.; Ni, Li-Ming; Kam, Chih-Min; Winkler, Ulrike; Johnson, David A.; Froelich, Christopher J.; Hudig, Dorothy; Powers, James C. [Journal of Medicinal Chemistry, 1998, vol. 41, # 13, p. 2289 - 2301]
[4]Sieńczyk, Marcin; Kliszczak, Maciej; Oleksyszyn, Józef [Tetrahedron Letters, 2006, vol. 47, # 25, p. 4209 - 4211]
[5]Current Patent Assignee: PROAXSIS LTD - US9340820, 2016, B2 Location in patent: Page/Page column 15; 16

4
[ 816-66-0 ]
[ 621-84-1 ]
[ 118609-93-1 ]

Reference： [1]Bulletin of the Chemical Society of Japan,1980,vol. 53,p. 2905 - 2909
[2]Chemistry Letters,1981,p. 1635 - 1638
[3]Organic Preparations and Procedures International,1997,vol. 29,p. 696 - 701

5
[ 759-05-7 ]
[ 621-84-1 ]
[ 95863-98-2 ]

Reference： [1]Acta Crystallographica, Section C: Crystal Structure Communications,2001,vol. 57,p. 1220 - 1221
[2]Journal of Molecular Structure,2003,vol. 654,p. 119 - 124
[3]Journal of Molecular Structure,2005,vol. 738,p. 189 - 192
[4]Agricultural and Biological Chemistry,1985,vol. 49,p. 2243 - 2246
[5]Organic Preparations and Procedures International,1997,vol. 29,p. 696 - 701
[6]Organic Letters,2005,vol. 7,p. 3405 - 3408

6
[ 15933-07-0 ]
[ 621-84-1 ]
[ 50685-03-5 ]

Reference： [1]Bulletin of the Chemical Society of Japan,1980,vol. 53,p. 2905 - 2909

7
[ 50461-74-0 ]
[ 621-84-1 ]
ethyl 2-(N-benzyloxycarbonylamino)-2-pentenoate [ No CAS ]

Reference： [1]Bulletin of the Chemical Society of Japan,1980,vol. 53,p. 2905 - 2909

8
[ 33170-72-8 ]
[ 621-84-1 ]
[ 14441-97-5 ]

Reference： [1]Journal of Heterocyclic Chemistry,1966,vol. 3,p. 459 - 461

9
[ 3920-50-1 ]
[ 621-84-1 ]
[1-(1H-Pyrazol-3-yl)-meth-(E)-ylidene]-carbamic acid benzyl ester [ No CAS ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,1995,vol. 104,p. 63 - 70

10
[ 621-84-1 ]
[ 18854-19-8 ]
[ 59524-07-1 ]

Reference： [1]Synthesis,1996,p. 1459 - 1462

11
[ 621-84-1 ]
[ 100-52-7 ]
[ 762-72-1 ]
[ 138723-71-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	With boron trifluoride diethyl etherate In acetonitrile at 0 - 20℃; for 2h;
95%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.166667h;
92%	In acetonitrile at 20℃; for 0.166667h;

92%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; for 10h; Inert atmosphere;
90%	With perrhenic acid anhydride In acetonitrile at 20℃; for 1h; chemoselective reaction;
83%	With scandium tris(trifluoromethanesulfonate) In acetonitrile at 25℃; for 2h;
83%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
83%	Stage #1: O-benzyl carbamate; benzaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 3h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
82%	With iodine In acetonitrile at 25℃; for 0.416667h;
80%	With iodine In acetonitrile at 20℃;
74%	In acetonitrile at 25℃; for 3h;
72%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; Inert atmosphere;
66%	With iodine; 1,1,1,3,3,3-hexamethyl-disilazane In acetonitrile Inert atmosphere; Schlenk technique;

Reference： [1]Veenstra, Siem J.; Schmid, Priska [Tetrahedron Letters, 1997, vol. 38, # 6, p. 997 - 1000]
[2]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[3]Smitha; Miriyala, Bruhaspathy; Williamson, John S. [Synlett, 2005, # 5, p. 839 - 841]
[4]Location in patent: scheme or table Pasunooti, Kalyan Kumar; Leow, Min Li; Vedachalam, Seenuvasan; Gorityala, Bala Kishan; Liu, Xue-Wei [Tetrahedron Letters, 2009, vol. 50, # 24, p. 2979 - 2981]
[5]Pramanik, Suman; Ghorai, Prasanta [Chemical Communications, 2012, vol. 48, # 12, p. 1820 - 1822]
[6]Kalita, Hima Rani; Phukan, Prodeep [Synthetic Communications, 2005, vol. 35, # 3, p. 475 - 481]
[7]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[8]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[9]Phukan, Prodeep [Journal of Organic Chemistry, 2004, vol. 69, # 11, p. 4005 - 4006]
[10]Borah, Arun Jyoti; Phukan, Prodeep [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 11, p. 1417 - 1424]
[11]Ollevier, Thierry; Ba, Tuya [Tetrahedron Letters, 2003, vol. 44, # 50, p. 9003 - 9005]
[12]Malkov, Andrei V.; Derrien, Nolwenn; Barlog, Maciej; Kocovsky, Pavel [Chemistry - A European Journal, 2014, vol. 20, # 16, p. 4542 - 4547]
[13]Bretzke, Sebastian; Scheeff, Stephan; Vollmeyer, Felicitas; Eberhagen, Friederike; Rominger, Frank; Menche, Dirk [Beilstein Journal of Organic Chemistry, 2016, vol. 12, p. 1111 - 1121]

12
[ 621-84-1 ]
[ 123-11-5 ]
[ 762-72-1 ]
benzyl (1-(4-methoxyphenyl)but-3-en-1-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.25h;
90%	In acetonitrile at 20℃; for 0.25h;
86%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

86%	Stage #1: O-benzyl carbamate; 4-methoxy-benzaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 2h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
85%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; for 8h; Inert atmosphere;
84%	With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 3h;
84%	With perrhenic acid anhydride In acetonitrile at 20℃; for 0.75h; chemoselective reaction;
83%	With scandium tris(trifluoromethanesulfonate) In acetonitrile at 25℃; for 3.5h;
81%	In acetonitrile at 25℃; for 6h;
79%	With iodine In acetonitrile at 25℃; for 0.25h;
75%	With iodine In acetonitrile at 20℃;
75%	With iodine In acetonitrile at 20℃; for 0.333333h;

Reference： [1]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[2]Smitha; Miriyala, Bruhaspathy; Williamson, John S. [Synlett, 2005, # 5, p. 839 - 841]
[3]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[4]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[5]Location in patent: scheme or table Pasunooti, Kalyan Kumar; Leow, Min Li; Vedachalam, Seenuvasan; Gorityala, Bala Kishan; Liu, Xue-Wei [Tetrahedron Letters, 2009, vol. 50, # 24, p. 2979 - 2981]
[6]Veenstra, Siem J.; Schmid, Priska [Tetrahedron Letters, 1997, vol. 38, # 6, p. 997 - 1000]
[7]Pramanik, Suman; Ghorai, Prasanta [Chemical Communications, 2012, vol. 48, # 12, p. 1820 - 1822]
[8]Kalita, Hima Rani; Phukan, Prodeep [Synthetic Communications, 2005, vol. 35, # 3, p. 475 - 481]
[9]Ollevier, Thierry; Ba, Tuya [Tetrahedron Letters, 2003, vol. 44, # 50, p. 9003 - 9005]
[10]Phukan, Prodeep [Journal of Organic Chemistry, 2004, vol. 69, # 11, p. 4005 - 4006]
[11]Borah, Arun Jyoti; Phukan, Prodeep [Journal of Chemical Sciences, 2013, vol. 125, # 6, p. 1503 - 1510]
[12]Borah, Arun Jyoti; Phukan, Prodeep [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 11, p. 1417 - 1424]

13
[ 621-84-1 ]
[ 78-84-2 ]
[ 762-72-1 ]
N-Benzyloxycarbonyl-2-methylhex-5-en-3-ylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.333333h;
78%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
78%	Stage #1: O-benzyl carbamate; isobutyraldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 3h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

74%	With iodine In acetonitrile at 25℃; for 0.25h;
70%	With boron trifluoride diethyl etherate In dichloromethane at 0 - 20℃; for 2h;
65%	With scandium tris(trifluoromethanesulfonate) In acetonitrile at 25℃; for 4.5h;
58%	In acetonitrile at 25℃; for 7h;

Reference： [1]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[2]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[3]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[4]Phukan, Prodeep [Journal of Organic Chemistry, 2004, vol. 69, # 11, p. 4005 - 4006]
[5]Veenstra, Siem J.; Schmid, Priska [Tetrahedron Letters, 1997, vol. 38, # 6, p. 997 - 1000]
[6]Kalita, Hima Rani; Phukan, Prodeep [Synthetic Communications, 2005, vol. 35, # 3, p. 475 - 481]
[7]Ollevier, Thierry; Ba, Tuya [Tetrahedron Letters, 2003, vol. 44, # 50, p. 9003 - 9005]

14
[ 621-84-1 ]
[ 100-52-7 ]
[ 39896-97-4 ]

Yield	Reaction Conditions	Operation in experiment
95%	With triethylsilane; trifluoroacetic acid In acetonitrile at 22℃; for 18h;
90%	With triethylsilane; perrhenic acid anhydride In dichloromethane at 20℃; for 1h; chemoselective reaction;

Reference： [1]Dube, Daniel; Scholte, Andrew A. [Tetrahedron Letters, 1999, vol. 40, # 12, p. 2295 - 2298]
[2]Das, Braja Gopal; Ghorai, Prasanta [Chemical Communications, 2012, vol. 48, # 66, p. 8276 - 8278]

15
[ 621-84-1 ]
[ 932-66-1 ]
1,2-trans-1-[2-(benzyloxycarbonylamino)cyclohexyl]ethan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	In dichloromethane at 20℃; for 36h;

Reference： [1]Gaunt, Matthew J.; Spencer, Jonathan B. [Organic Letters, 2001, vol. 3, # 1, p. 25 - 28]

16
[ 621-84-1 ]
[ 68471-57-8 ]
benzyl 2-[(benzyloxycarbonyl)amino]-3-iodo-1-pyrrolidinecarboxylate [ No CAS ]

Reference： [1]Tetrahedron Letters,2001,vol. 42,p. 7007 - 7010
[2]Tetrahedron,2005,vol. 61,p. 1221 - 1244

17
[ 17082-61-0 ]
[ 621-84-1 ]
[ 406951-43-7 ]

Yield	Reaction Conditions	Operation in experiment
81%	With hydrogenchloride In diethyl ether at 80℃; for 4h;
70%	With hydrogenchloride In 1,4-dioxane; diethyl ether at 0 - 80℃; for 4h; Sealed tube;	169.1 Step 1: Benzyl N-(2-oxocyclobutyl)carbamate In a sealed tube, 1,2-bis(trimethylsiloxy)cyclobutene (2 g, 8.6786 mmol) was added to benzyl carbamate (1.6 g, 5.3872 mL, 10.585 mmol) in HCl (in diethylether) (30 mL of 2 M, 60.000 mmol) at 0 °C. The sealed tube was capped and heated at 80 °C for 4 h. The tube was cooled to 0 °C before opening it. The content was concentrated under reduced pressure and the resulting residue was purified on silica gel using a 0 to 50% ethyl acetate in heptanes to provide benzyl N-(2-oxocyclobutyl)carbamate (1.4 g, 70%) as a clear yellow oil 1H NMR (400 MHz, CDCl3) δ 7.39 - 7.33 (m, 5H), 5.40 - 5.20 (m, 1H), 5.11 (s, 2H), 4.89 (q, J = 8.5 Hz, 1H), 3.01 - 2.79 (m, 2H), 2.54 - 2.38 (m, 1H), 2.10 - 1.97 (m, 1H). ESI-MS m/z calc.219.08954, found 220.2 (M+1)+; Retention time: 1.55 minutes; LC method X.
	With hydrogenchloride In diethyl ether at 0℃; for 4h; Reflux;

Reference： [1]Lall, Manjinder S.; Ramtohul, Yeeman K.; James, Michael N.G.; Vederas, John C. [Journal of Organic Chemistry, 2002, vol. 67, # 5, p. 1536 - 1547]
[2]Current Patent Assignee: VERTEX PHARMACEUTICALS (OLD) - WO2022/76622, 2022, A2 Location in patent: Paragraph 00888
[3]Location in patent: scheme or table Duranti, Andrea; Tontini, Andrea; Antonietti, Francesca; Vacondio, Federica; Fioni, Alessandro; Silva, Claudia; Lodola, Alessio; Rivara, Silvia; Solorzano, Carlos; Piomelli, Daniele; Tarzia, Giorgio; Mor, Marco [Journal of Medicinal Chemistry, 2012, vol. 55, # 10, p. 4824 - 4836]

18
[ 816-66-0 ]
[ 621-84-1 ]
[ 118609-93-1 ]

Reference： [1]Acta Crystallographica, Section C: Crystal Structure Communications,2002,vol. 58,p. o212-o214

19
[ 621-84-1 ]
[ 2043-21-2 ]
3-[3-(benzyloxycarbonylamino)propionyl]oxazolidin-2-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
49%	With bis(trifluoromethanesulfonyl)amide In acetonitrile at -20℃; for 72h;

Reference： [1]Wabnitz, Tobias C.; Spencer, Jonathan B. [Organic Letters, 2003, vol. 5, # 12, p. 2141 - 2144] Wabnitz, Tobias C.; Yu, Jin-Quan; Spencer, Jonathan B. [Chemistry - A European Journal, 2004, vol. 10, # 2, p. 484 - 493]

20
[ 621-84-1 ]
[ 932-66-1 ]
1,2-trans-1-[2-(benzyloxycarbonylamino)cyclohexyl]ethan-1-one [ No CAS ]
1,2-cis-1-[2-(benzyloxycarbonylamino)cyclohexyl]ethan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
1: 77% 2: 4%	With bis(trifluoromethanesulfonyl)amide In acetonitrile at -20℃; for 12h;

Reference： [1]Wabnitz, Tobias C.; Spencer, Jonathan B. [Organic Letters, 2003, vol. 5, # 12, p. 2141 - 2144]

21
[ 621-84-1 ]
[ 104-88-1 ]
[ 762-72-1 ]
benzyl (1-(4-chlorophenyl)but-3-en-1-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
82%	With perrhenic acid anhydride In acetonitrile at 20℃; for 1h; chemoselective reaction;
78%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
78%	Stage #1: O-benzyl carbamate; 4-chlorobenzaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 3.5h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

75%	In acetonitrile at 25℃; for 4h;
70%	With iodine In acetonitrile at 20℃;
70%	With iodine In acetonitrile at 20℃; for 0.333333h;

Reference： [1]Pramanik, Suman; Ghorai, Prasanta [Chemical Communications, 2012, vol. 48, # 12, p. 1820 - 1822]
[2]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[3]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[4]Ollevier, Thierry; Ba, Tuya [Tetrahedron Letters, 2003, vol. 44, # 50, p. 9003 - 9005]
[5]Borah, Arun Jyoti; Phukan, Prodeep [Journal of Chemical Sciences, 2013, vol. 125, # 6, p. 1503 - 1510]
[6]Borah, Arun Jyoti; Phukan, Prodeep [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 11, p. 1417 - 1424]

22
[ 621-84-1 ]
[ 2043-61-0 ]
[ 762-72-1 ]
[ 646480-73-1 ]

Yield	Reaction Conditions	Operation in experiment
96%	With perrhenic acid anhydride In acetonitrile at 20℃; for 0.3h; chemoselective reaction;
89%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.333333h;
86%	In acetonitrile at 25℃; for 23h;

76%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
76%	Stage #1: O-benzyl carbamate; cyclohexanecarbaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 5h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

Reference： [1]Pramanik, Suman; Ghorai, Prasanta [Chemical Communications, 2012, vol. 48, # 12, p. 1820 - 1822]
[2]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[3]Ollevier, Thierry; Ba, Tuya [Tetrahedron Letters, 2003, vol. 44, # 50, p. 9003 - 9005]
[4]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[5]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]

23
[ 123-73-9 ]
[ 621-84-1 ]
[ 623-91-6 ]
3-benzyloxycarbonylamino-cyclohex-4-ene-1,2-dicarboxylic acid diethyl ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	With toluene-4-sulfonic acid In 1-methyl-pyrrolidin-2-one at 120℃; for 24h;

Reference： [1]Neumann, Helfried; Von Wangelin, Axel Jacobi; Klaus, Stefan; Struebing, Dirk; Goerdes, Dirk; Beller, Matthias [Angewandte Chemie - International Edition, 2003, vol. 42, # 37, p. 4503 - 4507]

24
[ 101-02-0 ]
[ 621-84-1 ]
[ 144072-30-0 ]
[ 695171-94-9 ]

Yield	Reaction Conditions	Operation in experiment
21%	With copper(II) bis(trifluoromethanesulfonate); In dichloromethane; at 20℃;	To a solution of <strong>[144072-30-0]tert-butyl 4-formylphenylcarbamate</strong> (3.81 mmol), benzyl carbamate (3.81 mmol) and triphenyl phosphite (3.81 mmol) in DCM (40 ml) was added Cu(OTf)2 (0.381 mmol). The resulting solution was stirred overnight at room temperature. The solvent was evaporated and the crude mixture was dissolved in MeOH, which was put overnight at -20 00. A precipitate was formed and filtered off.Yield: 21%1H-NMR (DMSO-d6, 400 MHz): 6 1.48 (s, 9H), 5.08 (m, 2H), 5.48 (m, 1H), 6.98 (d, J=7.6 Hz, 2H), 7.05 (d, J=8.0 Hz, 2H), 7.19 (m, 2H), 7.35 (m, 9H), 7.49 (m, 4H), 8.10 (d, J=9.6 Hz, 1H), 9.41 (s, 1H)

Reference： [1]Synthesis,2005,p. 634 - 638
[2]Journal of Medicinal Chemistry,2004,vol. 47,p. 2411 - 2413
[3]Patent: WO2015/144933,2015,A1 .Location in patent: Page/Page column 34

25
[ 101-02-0 ]
[ 621-84-1 ]
[ 144072-30-0 ]
[ 695171-95-0 ]

Reference： [1]Journal of Medicinal Chemistry,2004,vol. 47,p. 2411 - 2413

26
[ 101-02-0 ]
[ 621-84-1 ]
[ 156866-52-3 ]
[ 695171-96-1 ]

Reference： [1]Journal of Medicinal Chemistry,2004,vol. 47,p. 2411 - 2413

27
[ 621-84-1 ]
[ 587-04-2 ]
[ 762-72-1 ]
N-benzyloxycarbonyl-1-(3-chlorophenyl)but-3-enylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
96%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.25h;
85%	With scandium tris(trifluoromethanesulfonate) In acetonitrile at 25℃; for 2.5h;
82%	With iodine In acetonitrile at 25℃; for 0.166667h;

74%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
74%	Stage #1: O-benzyl carbamate; m-Chlorobenzaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 3h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

Reference： [1]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[2]Kalita, Hima Rani; Phukan, Prodeep [Synthetic Communications, 2005, vol. 35, # 3, p. 475 - 481]
[3]Phukan, Prodeep [Journal of Organic Chemistry, 2004, vol. 69, # 11, p. 4005 - 4006]
[4]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[5]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]

28
[ 621-84-1 ]
[ 1122-91-4 ]
[ 762-72-1 ]
N-benzyloxycarbonyl-1-(4-bromophenyl)but-3-enylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
89%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.333333h;
88%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; for 8h; Inert atmosphere;
80%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

80%	Stage #1: O-benzyl carbamate; 4-bromo-benzaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 3h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
78%	With iodine In acetonitrile at 25℃; for 0.166667h;
78%	With scandium tris(trifluoromethanesulfonate) In acetonitrile at 25℃; for 3h;
75%	With iodine In acetonitrile at 20℃;
75%	With iodine In acetonitrile at 20℃; for 0.333333h;

Reference： [1]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[2]Location in patent: scheme or table Pasunooti, Kalyan Kumar; Leow, Min Li; Vedachalam, Seenuvasan; Gorityala, Bala Kishan; Liu, Xue-Wei [Tetrahedron Letters, 2009, vol. 50, # 24, p. 2979 - 2981]
[3]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[4]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[5]Phukan, Prodeep [Journal of Organic Chemistry, 2004, vol. 69, # 11, p. 4005 - 4006]
[6]Kalita, Hima Rani; Phukan, Prodeep [Synthetic Communications, 2005, vol. 35, # 3, p. 475 - 481]
[7]Borah, Arun Jyoti; Phukan, Prodeep [Journal of Chemical Sciences, 2013, vol. 125, # 6, p. 1503 - 1510]
[8]Borah, Arun Jyoti; Phukan, Prodeep [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 11, p. 1417 - 1424]

29
[ 930-88-1 ]
[ 30446-99-2 ]
[ 621-84-1 ]
[ 768370-20-3 ]

Reference： [1]Zeitschrift fur Naturforschung, B: Chemical Sciences,2004,vol. 59,p. 431 - 438

30
[ 621-84-1 ]
[ 17763-95-0 ]
[ 19402-87-0 ]
[ 86-74-8 ]
benzyl 9H-carbazole-9-carboxylate [ No CAS ]

Reference： [1]Journal of Organic Chemistry,2005,vol. 70,p. 413 - 419

31
[ 621-84-1 ]
[ 100-52-7 ]
[ 98-86-2 ]
3-(N-benzyloxycarbonylamino)-1,3-diphenylpropan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With hafnium tetrakis(trifluoromethanesulfonate) In neat (no solvent) at 80℃; for 2h;	3.2. General Synthetic Procedure and Characterization of β-Carbamate Ketones General procedure: Hf(OTf)4 (0.04 mmol, 0.02 eq.) was added to a mixture of aldehyde (2 mmol, 1.0 eq.),ketone (2 mmol, 1.0 eq.), and carbamate (3 mmol, 1.5 eq.) in an open glass vial (10 mL). The reaction was stirred at 80°C in an aluminum heating module for 2-4 h. The reaction mixture was cooled, dissolved in CH2Cl2 (1 mL), and loaded on a silica gel column. Flash column chromatography (PE/EA = 5:1) afforded products 1-20 in pure form.
89%	With dimethylbromosulphonium bromide In acetonitrile at 20℃; for 1h;
82%	With phosphotungstic acid In acetonitrile at 20℃; for 24h;

80%	With dibromotriphenylphosphorane In neat (no solvent) at 20℃; for 12h;	General procedure: Triphenylphosphine dibromide (5 mol%) was added to a mixture of benzaldehyde (1 mmol), carbamate (1 mmol), andacetophenone (1 mmol), and the reaction mixture was stirred at roomtemperature. The progress of the reaction was monitored by TLC. Aftercompletion of the reaction, the reaction mixture was extracted with EtOAc(2 x 10 mL), dried over anhydrous Na2SO4, and concentrated and purified bycolumn chromatography on silica gel (60-120 mesh) with petroleum ether-EtOAc as eluent.
78%	With iodine In acetonitrile at 20℃; for 24h;
72%	With chloro-trimethyl-silane; iron(III) chloride In diethyl ether; dichloromethane at 25℃; for 15h;
	With gold(III) chloride; triphenylphosphine In acetonitrile at 20℃; for 24h;

Reference： [1]Chen, Zhen-Zhen; Chi, Mei; Dong, Ying-Ying; Pu, Shou-Zhi; Sun, Qi; Yang, Dong-Zhao [Molecules, 2022, vol. 27, # 3]
[2]Das, Biswanath; Majhi, Anjoy; Chowdhury, Nikhil; Reddy, Kongara Ravinder; Ravikanth, Bommena [Chemistry Letters, 2007, vol. 36, # 9, p. 1106 - 1107]
[3]Wang, Rui; Huang, Taikun; Shi, Lin; Li, Bogang; Lu, Xiaoxia [Synlett, 2007, # 14, p. 2197 - 2200]
[4]Buragohain, Pori; Saikia, Partha Pratim; Barua, Nabin C. [Tetrahedron Letters, 2013, vol. 54, # 27, p. 3562 - 3564]
[5]Phukan, Prodeep; Kataki, Dolly; Chakraborty, Pranita [Tetrahedron Letters, 2006, vol. 47, # 31, p. 5523 - 5525]
[6]Xu, Li-Wen; Wang, Zong-Ting; Xia, Chun-Gu; Li, Lyi; Zhao, Pei-Qing [Helvetica Chimica Acta, 2004, vol. 87, # 10, p. 2608 - 2612]
[7]Xu, Li-Wen; Xia, Chun-Gu; Li, Lyi [Journal of Organic Chemistry, 2004, vol. 69, # 24, p. 8482 - 8484]

32
[ 621-84-1 ]
[ 104-87-0 ]
[ 762-72-1 ]
N-benzyloxycarbonyl-1-(4-methylphenyl)but-3-enylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.166667h;
90%	In acetonitrile at 20℃; for 0.166667h;
90%	With copper(II) bis(trifluoromethanesulfonate) In acetonitrile at 20℃; for 8h; Inert atmosphere;

90%	With perrhenic acid anhydride In acetonitrile at 20℃; for 0.5h; chemoselective reaction;
82%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
82%	Stage #1: O-benzyl carbamate; 4-methyl-benzaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 2.5h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
72%	With iodine In acetonitrile at 20℃;
72%	With iodine In acetonitrile at 20℃; for 0.333333h;

Reference： [1]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[2]Smitha; Miriyala, Bruhaspathy; Williamson, John S. [Synlett, 2005, # 5, p. 839 - 841]
[3]Location in patent: scheme or table Pasunooti, Kalyan Kumar; Leow, Min Li; Vedachalam, Seenuvasan; Gorityala, Bala Kishan; Liu, Xue-Wei [Tetrahedron Letters, 2009, vol. 50, # 24, p. 2979 - 2981]
[4]Pramanik, Suman; Ghorai, Prasanta [Chemical Communications, 2012, vol. 48, # 12, p. 1820 - 1822]
[5]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[6]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[7]Borah, Arun Jyoti; Phukan, Prodeep [Journal of Chemical Sciences, 2013, vol. 125, # 6, p. 1503 - 1510]
[8]Borah, Arun Jyoti; Phukan, Prodeep [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2014, vol. 53B, # 11, p. 1417 - 1424]

33
[ 621-84-1 ]
[ 104-87-0 ]
[ 99-91-2 ]
benzyl N-[3-(4-chlorophenyl)-1-(4-methylphenyl)-3-oxopropyl]carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With hafnium tetrakis(trifluoromethanesulfonate) In neat (no solvent) at 80℃; for 2h;	3.2. General Synthetic Procedure and Characterization of β-Carbamate Ketones General procedure: Hf(OTf)4 (0.04 mmol, 0.02 eq.) was added to a mixture of aldehyde (2 mmol, 1.0 eq.),ketone (2 mmol, 1.0 eq.), and carbamate (3 mmol, 1.5 eq.) in an open glass vial (10 mL). The reaction was stirred at 80°C in an aluminum heating module for 2-4 h. The reaction mixture was cooled, dissolved in CH2Cl2 (1 mL), and loaded on a silica gel column. Flash column chromatography (PE/EA = 5:1) afforded products 1-20 in pure form.
69%	With dimethylbromosulphonium bromide In acetonitrile at 20℃; for 1h;
66%	With iodine In acetonitrile at 20℃; for 24h;

Reference： [1]Chen, Zhen-Zhen; Chi, Mei; Dong, Ying-Ying; Pu, Shou-Zhi; Sun, Qi; Yang, Dong-Zhao [Molecules, 2022, vol. 27, # 3]
[2]Das, Biswanath; Majhi, Anjoy; Chowdhury, Nikhil; Reddy, Kongara Ravinder; Ravikanth, Bommena [Chemistry Letters, 2007, vol. 36, # 9, p. 1106 - 1107]
[3]Phukan, Prodeep; Kataki, Dolly; Chakraborty, Pranita [Tetrahedron Letters, 2006, vol. 47, # 31, p. 5523 - 5525]

34
[ 621-84-1 ]
[ 104-88-1 ]
[ 98-86-2 ]
3-(N-benzyloxycarbonylamino)-3-(4-chlorophenyl)-1-phenylpropan-1-one [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
88%	With hafnium tetrakis(trifluoromethanesulfonate) In neat (no solvent) at 80℃; for 2h;	3.2. General Synthetic Procedure and Characterization of β-Carbamate Ketones General procedure: Hf(OTf)4 (0.04 mmol, 0.02 eq.) was added to a mixture of aldehyde (2 mmol, 1.0 eq.),ketone (2 mmol, 1.0 eq.), and carbamate (3 mmol, 1.5 eq.) in an open glass vial (10 mL). The reaction was stirred at 80°C in an aluminum heating module for 2-4 h. The reaction mixture was cooled, dissolved in CH2Cl2 (1 mL), and loaded on a silica gel column. Flash column chromatography (PE/EA = 5:1) afforded products 1-20 in pure form.
87%	With dimethylbromosulphonium bromide In acetonitrile at 20℃; for 1h;
84%	With phosphotungstic acid In acetonitrile at 20℃; for 24h;

78%

With iodine In acetonitrile at 20℃; for 24h;

Reference： [1]Chen, Zhen-Zhen; Chi, Mei; Dong, Ying-Ying; Pu, Shou-Zhi; Sun, Qi; Yang, Dong-Zhao [Molecules, 2022, vol. 27, # 3]
[2]Das, Biswanath; Majhi, Anjoy; Chowdhury, Nikhil; Reddy, Kongara Ravinder; Ravikanth, Bommena [Chemistry Letters, 2007, vol. 36, # 9, p. 1106 - 1107]
[3]Wang, Rui; Huang, Taikun; Shi, Lin; Li, Bogang; Lu, Xiaoxia [Synlett, 2007, # 14, p. 2197 - 2200]
[4]Phukan, Prodeep; Kataki, Dolly; Chakraborty, Pranita [Tetrahedron Letters, 2006, vol. 47, # 31, p. 5523 - 5525]

35
[ 621-84-1 ]
[ 99-91-2 ]
[ 100-52-7 ]
benzyl N-[3-(4-chlorophenyl)-1-phenyl-3-oxopropyl]carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	With hafnium tetrakis(trifluoromethanesulfonate) In neat (no solvent) at 80℃; for 2h;	3.2. General Synthetic Procedure and Characterization of β-Carbamate Ketones General procedure: Hf(OTf)4 (0.04 mmol, 0.02 eq.) was added to a mixture of aldehyde (2 mmol, 1.0 eq.),ketone (2 mmol, 1.0 eq.), and carbamate (3 mmol, 1.5 eq.) in an open glass vial (10 mL). The reaction was stirred at 80°C in an aluminum heating module for 2-4 h. The reaction mixture was cooled, dissolved in CH2Cl2 (1 mL), and loaded on a silica gel column. Flash column chromatography (PE/EA = 5:1) afforded products 1-20 in pure form.
80%	With dibromotriphenylphosphorane In neat (no solvent) at 20℃; for 12h;	General procedure: Triphenylphosphine dibromide (5 mol%) was added to a mixture of benzaldehyde (1 mmol), carbamate (1 mmol), andacetophenone (1 mmol), and the reaction mixture was stirred at roomtemperature. The progress of the reaction was monitored by TLC. Aftercompletion of the reaction, the reaction mixture was extracted with EtOAc(2 x 10 mL), dried over anhydrous Na2SO4, and concentrated and purified bycolumn chromatography on silica gel (60-120 mesh) with petroleum ether-EtOAc as eluent.
73%	With dimethylbromosulphonium bromide In acetonitrile at 20℃; for 1h;

65%

With iodine In acetonitrile at 20℃; for 24h;

Reference： [1]Chen, Zhen-Zhen; Chi, Mei; Dong, Ying-Ying; Pu, Shou-Zhi; Sun, Qi; Yang, Dong-Zhao [Molecules, 2022, vol. 27, # 3]
[2]Buragohain, Pori; Saikia, Partha Pratim; Barua, Nabin C. [Tetrahedron Letters, 2013, vol. 54, # 27, p. 3562 - 3564]
[3]Das, Biswanath; Majhi, Anjoy; Chowdhury, Nikhil; Reddy, Kongara Ravinder; Ravikanth, Bommena [Chemistry Letters, 2007, vol. 36, # 9, p. 1106 - 1107]
[4]Phukan, Prodeep; Kataki, Dolly; Chakraborty, Pranita [Tetrahedron Letters, 2006, vol. 47, # 31, p. 5523 - 5525]

36
[ 621-84-1 ]
[ 99-90-1 ]
[ 100-52-7 ]
benzyl N-[3-(4-bromophenyl)-1-phenyl-3-oxopropyl]carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With hafnium tetrakis(trifluoromethanesulfonate) In neat (no solvent) at 80℃; for 2h;	3.2. General Synthetic Procedure and Characterization of β-Carbamate Ketones General procedure: Hf(OTf)4 (0.04 mmol, 0.02 eq.) was added to a mixture of aldehyde (2 mmol, 1.0 eq.),ketone (2 mmol, 1.0 eq.), and carbamate (3 mmol, 1.5 eq.) in an open glass vial (10 mL). The reaction was stirred at 80°C in an aluminum heating module for 2-4 h. The reaction mixture was cooled, dissolved in CH2Cl2 (1 mL), and loaded on a silica gel column. Flash column chromatography (PE/EA = 5:1) afforded products 1-20 in pure form.
77%	With dimethylbromosulphonium bromide In acetonitrile at 20℃; for 1h;
70%	With iodine In acetonitrile at 20℃; for 24h;

70%

With dibromotriphenylphosphorane In neat (no solvent) at 20℃; for 12h;

General procedure: Triphenylphosphine dibromide (5 mol%) was added to a mixture of benzaldehyde (1 mmol), carbamate (1 mmol), andacetophenone (1 mmol), and the reaction mixture was stirred at roomtemperature. The progress of the reaction was monitored by TLC. Aftercompletion of the reaction, the reaction mixture was extracted with EtOAc(2 x 10 mL), dried over anhydrous Na2SO4, and concentrated and purified bycolumn chromatography on silica gel (60-120 mesh) with petroleum ether-EtOAc as eluent.

Reference： [1]Chen, Zhen-Zhen; Chi, Mei; Dong, Ying-Ying; Pu, Shou-Zhi; Sun, Qi; Yang, Dong-Zhao [Molecules, 2022, vol. 27, # 3]
[2]Das, Biswanath; Majhi, Anjoy; Chowdhury, Nikhil; Reddy, Kongara Ravinder; Ravikanth, Bommena [Chemistry Letters, 2007, vol. 36, # 9, p. 1106 - 1107]
[3]Phukan, Prodeep; Kataki, Dolly; Chakraborty, Pranita [Tetrahedron Letters, 2006, vol. 47, # 31, p. 5523 - 5525]
[4]Buragohain, Pori; Saikia, Partha Pratim; Barua, Nabin C. [Tetrahedron Letters, 2013, vol. 54, # 27, p. 3562 - 3564]

37
[ 621-84-1 ]
[ 98-86-2 ]
[ 135-02-4 ]
benzyl (1-(2-methoxyphenyl)-3-oxo-3-phenylpropyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With hafnium tetrakis(trifluoromethanesulfonate) In neat (no solvent) at 80℃; for 2h;	3.2. General Synthetic Procedure and Characterization of β-Carbamate Ketones General procedure: Hf(OTf)4 (0.04 mmol, 0.02 eq.) was added to a mixture of aldehyde (2 mmol, 1.0 eq.),ketone (2 mmol, 1.0 eq.), and carbamate (3 mmol, 1.5 eq.) in an open glass vial (10 mL). The reaction was stirred at 80°C in an aluminum heating module for 2-4 h. The reaction mixture was cooled, dissolved in CH2Cl2 (1 mL), and loaded on a silica gel column. Flash column chromatography (PE/EA = 5:1) afforded products 1-20 in pure form.
82%	With phosphotungstic acid In acetonitrile at 20℃; for 24h;
78%	With iodine In acetonitrile at 20℃; for 24h;

Reference： [1]Chen, Zhen-Zhen; Chi, Mei; Dong, Ying-Ying; Pu, Shou-Zhi; Sun, Qi; Yang, Dong-Zhao [Molecules, 2022, vol. 27, # 3]
[2]Wang, Rui; Huang, Taikun; Shi, Lin; Li, Bogang; Lu, Xiaoxia [Synlett, 2007, # 14, p. 2197 - 2200]
[3]Phukan, Prodeep; Kataki, Dolly; Chakraborty, Pranita [Tetrahedron Letters, 2006, vol. 47, # 31, p. 5523 - 5525]

38
[ 621-84-1 ]
[ 62668-02-4 ]
[ 928765-35-9 ]

Yield	Reaction Conditions	Operation in experiment
98%	With C₃₆H₄₀O₂₀S₄ In water at 60℃; for 24h;
97%	With potassium hexafluorophosphate; bismuth(lll) trifluoromethanesulfonate; calcium sulfate In 1,4-dioxane at 23 - 26℃; for 0.2h;
94%	With sodium tetrachloroaurate(III) dihyrate In dichloromethane for 1h; Reflux;

94%	With iodine In acetonitrile at 20℃; for 14h;
93%	With (triphenyl phosphite)gold(I) chloride; silver trifluoromethanesulfonate In 1,4-dioxane at 25℃; for 1h; Inert atmosphere; Darkness; regioselective reaction;
92%	With calcium sulfate; iodine In dichloromethane at 20℃; for 3h;
92%	With trifluorormethanesulfonic acid In 1,4-dioxane at 25℃; for 24h;
92%	With aluminium(III) triflate In nitromethane at 20℃; for 0.166667h;
89%	at 50℃; for 24h;

Reference： [1]Location in patent: scheme or table Shirakawa, Seiji; Shimizu, Shoichi [Synlett, 2008, # 10, p. 1539 - 1542]
[2]Qin, Hongbo; Yamagiwa, Noriyuki; Matsunaga, Shigeki; Shibasaki, Masakatsu [Angewandte Chemie - International Edition, 2007, vol. 46, # 3, p. 409 - 413]
[3]Ohshima, Takashi; Nakahara, Yasuhito; Ipposhi, Junji; Miyamoto, Yoshiki; Mashima, Kazushi [Chemical Communications, 2011, vol. 47, # 29, p. 8322 - 8324]
[4]Location in patent: experimental part Liu, Zhe; Wang, Dong; Chen, Yongjun [Letters in Organic Chemistry, 2011, vol. 8, # 1, p. 73 - 80]
[5]Location in patent: experimental part Giner, Xavier; Trillo, Paz; Nájera, Carmen [Journal of Organometallic Chemistry, 2011, vol. 696, # 1, p. 357 - 361]
[6]Wu, Wenhan; Rao, Weidong; Er, Ya Qin; Loh, Joanna Kejun; Poh, Chai Yun; Chan, Philip Wai Hong [Tetrahedron Letters, 2008, vol. 49, # 16, p. 2620 - 2624]
[7]Location in patent: experimental part Trillo, Paz; Baeza, Alejandro; Najera, Carmen [European Journal of Organic Chemistry, 2012, # 15, p. 2929 - 2934]
[8]Ohshima, Takashi; Ipposhi, Junji; Nakahara, Yasuhito; Shibuya, Ryozo; Mashima, Kazushi [Advanced Synthesis and Catalysis, 2012, vol. 354, # 13, p. 2447 - 2452]
[9]Trillo, Paz; Baeza, Alejandro; Najera, Carmen [Journal of Organic Chemistry, 2012, vol. 77, # 17, p. 7344 - 7354]

39
[ 939-18-4 ]
[ 621-84-1 ]
benzyl (coumarin-3-yl)carbamate [ No CAS ]
[ 91-64-5 ]

Reference： [1]Tetrahedron Letters,2007,vol. 48,p. 6928 - 6932

40
[ 621-84-1 ]
[ 69901-75-3 ]

Reference： [1]Organic Letters,2005,vol. 7,p. 3405 - 3408

41
[ 621-84-1 ]
[ 69901-85-5 ]

Reference： [1]Organic Letters,2005,vol. 7,p. 3405 - 3408

42
[ 621-84-1 ]
[ 118247-68-0 ]

Yield	Reaction Conditions	Operation in experiment
	Multi-step reaction with 2 steps 1.1: 2,2'-isopropylidene bis[(4S)-4-tert-butyl-2-oxazoline]; Cu(OTf)2 / CH₂Cl₂ / 0.5 h / 20 °C 1.2: 71 percent / CH₂Cl₂ / 68 h / 20 °C 2.1: 91 percent / aq. NaIO₄ / methanol / 20 °C

Reference： [1]Palomo, Claudio; Oiarbide, Mikel; Halder, Rajkumar; Kelso, Michael; Gomez-Bengoa, Enrique; Garcia, Jesus M. [Journal of the American Chemical Society, 2004, vol. 126, # 30, p. 9188 - 9189]

43
[ 621-84-1 ]
[ 18605-26-0 ]

Reference： [1]Journal of Organic Chemistry,2002,vol. 67,p. 4957 - 4959

44
[ 50-00-0 ]
[ 621-84-1 ]
[ 31037-42-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium carbonate In water at 20 - 65℃; for 26h; Cooling with ice;
74%	With water; sodium carbonate In water at 20℃;
74%	With sodium carbonate In water at 20℃; Heating;	4.2.2. Synthesis of benzyl N-(hydroxymethyl)-carbamate (1) Benzyl carbamate (6.0 g, 40 mmol) was added to a solution of 37% formalin (4.4 g, 56 mmol) and sodium carbonate (2.2 g,20 mmol) in 65 mL water. The mixture was heated until all the solids were dissolved, then cooled to room temperature and stirred overnight. The precipitated solid was then filtered, dried, and redissolved in dichloromethane. The solution was dried using anhydrous magnesium sulfate and the solvent was removed under vacuum to give the product as a white solid which was used in the next step without further purification (5.4 g, 74%) 1H NMR (CDCl3) δ 4.10 (s, 1H), 4.71 (d, J 6.5 Hz, 2H), 5.13 (s, 2H), 6.07 (s, 1H), 7.36 (s,5H); m/z (LCMS, ESI): calc. for [M+H]+ 182.1; found 182.2.

73%	With sodium carbonate In water at 20℃; Reflux;
64%	With potassium carbonate In water at 65℃; for 0.75h;
44%	With potassium carbonate In water at 60℃; for 0.5h;
	With sodium carbonate In water at 20 - 60℃; for 3.5h;
	With sodium carbonate In water at 20℃;
	With acetic acid at 50℃; for 4h;	Benzyl [Bis(allyloxy)phosphoryl]methyl}carbamate (2) Benzyl carbamate (1) (756 mg, 5.00 mmol, 1.0 equiv) and paraformaldehyde (180 mg, 6.00 mmol, 1.2 equiv) were suspended in AcOH and heated to 50 °C for 4 h. The solvent was removed under reduced pressure and triallyl phosphite (2.02 g, 10.00 mmol, 2.0 equiv) was added to the residue. The mixture was heated at 110 °C for 14 h. All volatile components were removed under reduced pressure and the crude product was purified by silica gel chromatography (cyclohexane/EtOAc,1:1). The product was obtained as a colorless oil (1.042 g, 3.20 mmol, 64%). 1H NMR (400 MHz, CDCl3): δ = 3.66 (dd, J = 11.2, 6.0 Hz, 2 H), 4.55 (dd,J = 7.6, 6.5 Hz, 4 H), 5.05 (s, 1 H), 5.11 (s, 2 H), 5.24 (dd, J = 10.4, 1.1 Hz, 2 H), 5.34 (dd, J = 17.1, 1.2 Hz, 2 H), 5.84-5.99 (m, 2 H), 7.28-7.41 (m, 5 H). 13C NMR (101 MHz, CDCl3): δ = 36.2, 37.8, 67.0, 67.1, 67.4, 118.7, 118.7, 128.3, 128.4, 128.7, 132.6, 132.6, 136.2, 156.2. 31P NMR (162 MHz, CDCl3): δ = 24.0. MS (ESI): m/z [M + H]+ calcd for C15H21NO5P: 326.31; found: 326.08.

Reference： [1]Meyer, Hartmut; Beck, Albert K.; Sebesta, Radovan; Seebach, Dieter; Denmark, Scott E.; Wilson, Tyler W. [Organic Syntheses, 2008, vol. 85, p. 287 - 294]
[2]Nasief, Nader N.; Hangauer, David [Journal of Medicinal Chemistry, 2014, vol. 57, # 6, p. 2315 - 2333]
[3]Nasief, Nader N.; Hangauer, David [European Journal of Medicinal Chemistry, 2015, vol. 90, p. 897 - 915]
[4]Weinstein, Adam B.; Schuman, David P.; Tan, Zhi Xu; Stahl, Shannon S. [Angewandte Chemie - International Edition, 2013, vol. 52, # 45, p. 11867 - 11870][Angew. Chem., 2013, vol. 125, # 45, p. 12083 - 12086]
[5]Location in patent: scheme or table Brocklehurst, Cara E.; Furegati, Markus; Mueller-Hartwieg, J. Constanze D.; Ossola, Flavio; La Vecchia, Luigi [Helvetica Chimica Acta, 2010, vol. 93, # 2, p. 314 - 323]
[6]Peddie, Victoria; Butcher, Raymond J.; Robinson, Ward T.; Wilce, Matthew C. J.; Traore, Daouda A. K.; Abell, Andrew D. [Chemistry - A European Journal, 2012, vol. 18, # 21, p. 6655 - 6662]
[7]Current Patent Assignee: PFIZER INC - US2004/266827, 2004, A1 Location in patent: Page 13
[8]Nasief, Nader N.; Tan, Hongwei; Kong, Jing; Hangauer, David [Journal of Medicinal Chemistry, 2012, vol. 55, # 19, p. 8283 - 8302]
[9]Cramer, Jonathan; Klebe, Gerhard [Synthesis, 2017, vol. 49, # 8, p. 1857 - 1866]

Yield	Reaction Conditions	Operation in experiment
		3-Carboxypyrid-2-one (5 g), diphenylphosphorylazide (9.9 g), benzyl alcohol (4.7 g), and triethylamine (3.6 g) were added to dioxane (50 mL). The mixture was allowed to stir at 90 C. for 20 h, was cooled, and the dioxane was evaporated. The residue was dissolved in ethyl acetate (400 mL), was washed (1N hydrochloric acid, brine), dried, evaporated and the resulting oil was purified by chromatography using ethyl acetate:dichloromethane (gradient, 0:100, 10:90, 20:80) as eluent to give the benzylcarbamate (6.2 g).

46
[ 333-93-7 ]
[ 501-53-1 ]
[ 621-84-1 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In water; N,N-dimethyl-formamide;	1,4-butanediamine dihydrochloride (5.96 g, 37 mmol) was dissolved in water (15 mL), and DMF (50 mL) was added. With rapid stirring, CBZ-Cl (1.0 mL, 7.0 mmol) was added dropwise over 2 minutes. The cloudy solution had pH~2.8. The pH was adjusted to 9.0 with 5N NaOH, (clear solution) and stirred for 2 hr. The reaction mixture was acidified to pH=1.25, extracted with ether (2), made basic (pH>10) with 5N NaOH, and extracted with dichloromethane (2). The dichloromethane fractions were combined and washed with water (2*), dried and evaporated in vacuo to provide the crude mono-CBZ amine (0.72 g, 3.24 mmol, 46%) which was used as is in the next step.

Reference： [1]Patent: US5583146,1996,A

47
[ 33630-99-8 ]
[ 501-53-1 ]
[ 621-84-1 ]
[ 3459-92-5 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium carbonate; In tetrahydrofuran;	b. 3-Benzyloxycarbonylaminopyrid-2-one. Benzyl chloroformate (13.085 g) was added dropwise to a stirred suspension of sodium carbonate (16.26 g) and <strong>[33630-99-8]3-aminopyrid-2-one</strong> (7.67 g) in tetrahydrofuran. The mixture was stirred overnight, poured into ethyl acetate (400 mL), washed (saturated aqueous sodium bicarbonate, brine), dried and evaporated. The resulting residue was purified by crystallization from methanol to give the benzyl carbonate as a white crystalline solid (10.7 g). The benzylcarbamate can alternatively be prepared as follows:

Reference： [1]Patent: US5521179,1996,A

48
[ 894493-95-9 ]
cis-N,N-dimethyl-1,2-cyclopentanediamine [ No CAS ]
[ 621-84-1 ]

Yield	Reaction Conditions	Operation in experiment
	Pd on carbon;	D. cis-N,N-dimethyl-1,2-cyclopentanediamine The benzyl carbamate obtained in the previous step C (7.9 g.,) was dissolved in 200 ml. ether, treated with 10% Pd on carbon (2.0 g.) and hydrogenated at Ca. 50 psi for 72 hours. The solution was filtered and the ether removed by distillation. The residue was distilled at reduced pressure to give 1.5 g., (7% overall yield) of the titled diamine, b.p. 90-100/30 mm. ir NH 3300; CH 2940, 2850; N-alkyl 2750; NH def 1590; CH 1460, 1440; CN/other 1350, 1265, 1200, 1140, 1105, 1070, 1040, 900; nmr (CDCl3) was in accord. Mass spectrum M+ 128.

Reference： [1]Patent: US4215114,1980,A

49
[ 621-84-1 ]
[ 154825-97-5 ]
[ 915084-42-3 ]

Reference： [1]Patent: WO2006/123639,2006,A1 .Location in patent: Page/Page column 138

50
[ 621-84-1 ]
[ 145691-52-7 ]
[ 915412-27-0 ]

Yield	Reaction Conditions	Operation in experiment
46%	Stage #1: O-benzyl carbamate; (3,5-dibromophenyl)(pyridin-3-yl)methanone With caesium carbonate In 1,4-dioxane; toluene at 20 - 80℃; for 0.583333h; Stage #2: at 105℃;	71 In a 1 L four neck flask equiped with a reflux condenser, a mechanical stirrer, and a thermometer were placed together 15.35 g (45.0 mmol) of (3,5-dibromo-phenyl)-pyridin-3-yl-methanone and 16.33 g (108.0 mmol) of benzyl carbamate. The flask was flushed under argon for 15 min. Then 20.50 g (63.0 mmol) of Cs2CO3 and 270 mL of dioxane were added. The flask was then heated to 80° C. internal temperature. In the mean time, in a 100 mL Schlenk were placed together 0.465 g of [Pd2(dba)3].CHCl3 (0.9 mmol Pd), 0.780 g Xantphos ligand (1.35 mmol) and 60 mL of a 1:4 toluene/dioxane mixture. The orange suspension thus obtained was stirred at room temperature for 20 min. Once the temperature in the large reaction flask reached 80° C., 10 mL of the Pd catalyst suspension were added. The reaction temperature was then increased to 105° C. internal temperature. In the following 5 h, more of the catalyst was added every hour by portions of 10 mL each. After refluxing overnight the reaction afforded a yellow solution and a brown precipitate. The reaction mixture was cooled down to room temperature and the precipitate filtered and washed with 3×50 mL of ethyl acetate. The yellow solution was evaporated to afford a yellow brown oil. The compound was purified by chromatography (900 g silica gel, 15:20:10:2 toluene/CH2Cl2/ethyl acetate/HCOOH) to yield a pale yellow oil. A further purification involved the precipitation of the product by dissolving the oil in a minimum of ethyl acetate and addition of hexane to yield 8.51 g (46%) 3-bromo-5-(pyridine-3-carbonyl)-phenyl]-carbamic acid benzyl ester as a white solid.
46%	With tris(dibenzylideneacetone)dipalladium⁽⁰⁾ chloroform complex; caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; sodium t-butanolate In 1,4-dioxane; toluene at 80℃; Inert atmosphere; Reflux;
46%	With caesium carbonate In 1,4-dioxane; toluene at 20 - 105℃; for 5.33333h;	71 3-Bromo-5-(pyridine-3-carbonyl)-phenyl]-carbamic acid benzyl esterIn a 1 L four neck flask equipped with a reflux condenser, a mechanical stirrer, and a thermometer were placed together 15.35 g (45.0 mmol) of (3,5-dibromo-phenyl)-pyridin-3-yl-methanone and 16.33 g (108.0 mmol) of benzyl carbamate. The flask was flushed under argon for 15 min. Then 20.50 g (63.0 mmol) of Cs2CO3 and 270 mL of dioxane were added. The flask was then heated to 80° C. internal temperature. In the mean time, in a 100 mL Schlenk were placed together 0.465 g of [Pd2(dba)3].CHCl3 (0.9 mmol Pd), 0.780 g Xantphos ligand (1.35 mmol) and 60 mL of a 1:4 toluene/dioxane mixture. The orange suspension thus obtained was stirred at room temperature for 20 min. Once the temperature in the large reaction flask reached 80° C., 10 mL of the Pd catalyst suspension were added. The reaction temperature was then increased to 105° C. internal temperature. In the following 5 h, more of the catalyst was added every hour by portions of 10 mL each. After refluxing overnight the reaction afforded a yellow solution and a brown precipitate. The reaction mixture was cooled down to room temperature and the precipitate filtered and washed with 3×50 mL of ethyl acetate. The yellow solution was evaporated to afford a yellow brown oil. The compound was purified by chromatography (900 g silica gel, 15:20:10:2 toluene/CH2Cl2/ethyl acetate/HCOOH) to yield a pale yellow oil. A further purification involved the precipitation of the product by dissolving the oil in a minimum of ethyl acetate and addition of hexane to yield 8.51 g (46%) 3-bromo-5-(pyridine-3-carbonyl)-phenyl]-carbamic acid benzyl ester as a white solid.

46%

With caesium carbonate In 1,4-dioxane; toluene at 80 - 105℃; Heating / reflux;

71 [0374] In a 1 L four neck flask equiped with a reflux condenser, a mechanical stirrer, and a thermometer were placed together 15.35 g (45.0 mmol) of (3,5- dibromo-phenyl)-pyridin-3-yl-methanone and 16.33 g (108.0 mmol) of benzyl carbamate. The flask was flushed under argon for 15 min. Then 20.50 g (63.0 mmol) of Cs2CO3 and 270 mL of dioxane were added. The flask was then heated to 80°C internal temperature. In the mean time, in a 100 mL Schlenk were placed together 0.465 g of [Pd2(dba)3] -CHCl3 (0.9 mmol Pd), 0.780 g Xantphos ligand (1.35 mmol) and 60 mL of a 1:4 toluene/dioxane mixture. The orange suspension thus obtained was stirred at room temperature for 20 min. Once the temperature in the large reaction flask reached 80°C, 10 mL of the Pd catalyst suspension were added. The reaction temperature was then increased to 1050C internal temperature. In the following 5 h, more of the catalyst was added every hour by portions of 10 mL each. After refluxing overnight the reaction afforded a yellow solution and a brown precipitate. The reaction mixture was cooled down to room temperature and the precipitate filtered and washed with 3 x 50 mL of ethyl acetate. The yellow solution was evaporated to afford a yellow brown oil. The compound was purified by chromatography (900 g silica gel, 15:20:10:2 toluene/CH2Cl2/ethyl acetate/HCOOH) to yield a pale yellow oil. A further purification involved the precipitation of the product by dissolving the oil in a minimum of ethyl acetate and addition of hexane to yield 8.51 g (46 %) 3-bromo-5-(pyridine-3- carbonyl)-phenyl]-carbamic acid benzyl ester as a white solid.

Reference： [1]Current Patent Assignee: LOCUS PHARMACEUTICALS, INC. - US2006/270686, 2006, A1 Location in patent: Page/Page column 43
[2]Location in patent: experimental part Shetty, Rupa S.; Lee, Younghee; Liu, Bin; Husain, Arifa; Joseph, Rhoda W.; Lu, Yixin; Nelson, David; Mihelcic, John; Chao, Wenchun; Moffett, Kristofer K.; Schumacher, Andreas; Flubacher, Dietmar; Stojanovic, Aleksandar; Bukhtiyarova, Marina; Williams, Ken; Lee, Kyoung-Jin; Ochman, Alexander R.; Saporito, Michael S.; Moore, William R.; Flynn, Gary A.; Dorsey, Bruce D.; Springman, Eric B.; Fujimoto, Ted; Kelly, Martha J. [Journal of Medicinal Chemistry, 2011, vol. 54, # 1, p. 179 - 200]
[3]Current Patent Assignee: LOCUS PHARMACEUTICALS, INC. - US2008/280891, 2008, A1 Location in patent: Page/Page column 42
[4]Current Patent Assignee: LOCUS PHARMACEUTICALS, INC. - WO2008/8059, 2008, A1 Location in patent: Page/Page column 121-122

51
[ 621-84-1 ]
[ 563-96-2 ]
[ 79002-45-2 ]

Yield	Reaction Conditions	Operation in experiment
100%	In toluene; at 40℃;	Step 1 : A solution of benzyl carbamate (90.0 g, 0.59 mol, 1.0 eq.) and monohydrate <strong>[563-96-2]dihydroxyacetic acid</strong> 1 (60.3 g, 1.1 mol, 1.1 eq.) in toluene (840 mL) was introduced in a 2 L flask and the solution was heated at 40C for 1.5 hours. Half of the solvent was concentrated down under reduce pressure. Toluene (540 mL) was added and half of the solvent was concentrated down under reduce pressure. Toluene (540 mL) was added and the reaction was stirred at 40C for 2 hours and then cooled down to 20C. The white solid was filtered, rinsed with toluene and dried under vacuum. The expected compound 2 (133.0 g, quant, yield, 95% purity (:H NMR)) was obtained as a white solid. :H NMR (400 MHz, DMSO-ds) : delta (ppm) : 5.05 (s, 2H), 5.21 (d, J = 8.8 Hz, 1H), 6.62-6.80 (br s, 1H), 7.26-7.44 (m, 5H), 8.14 (d, J= 8.8 Hz, 1H), 12.10-13.60 (br s, 1H).

Reference： [1]Patent: WO2016/46409,2016,A1 .Location in patent: Paragraph 00174
[2]Journal of Medicinal Chemistry,2018,vol. 61,p. 7814 - 7826
[3]Organic Process Research and Development,2011,vol. 15,p. 1348 - 1357
[4]Journal of Organic Chemistry,2008,vol. 73,p. 1661 - 1681

52
[ 621-84-1 ]
[ 591-31-1 ]
[ 135-19-3 ]
[ 1071838-63-5 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sodium hydrogen sulfate; silica gel at 100℃; for 3h;
94%	With nano-silica-bonded 3-(n-propyl)-1-sulfoimidazolium chloride In neat (no solvent) at 70℃; for 0.333333h;	General procedure for the production of α-carbamatoalkyl-β-naphthols To a mixture of β-naphthol (0.144 g, 1 mmol), arylaldehyde (1 mmol) and alkylcarbamate (1.3 mmol) in a test tube, was added nano-SB-[PSIM]Cl (0.01 g), and the resulting mixture was stirred magnetically at 70 °C, and after solidification of the reaction mixture with a small rod at that temperature. The mixture was cooled to room temperature, then warm EtOAc (5 mL) was added and stirred for 1 min followed by centrifugation and decanting to separate nano-SB-[PSIM]Cl (the silica-bonded IL is not soluble in warm EtOAc, but the unreacted starting materials and the product are soluble in it). The separated EtOAc was evaporated, and the solid residue was recrystallized from hot EtOH (95 %) to give the pure α-carbamatoalkyl-β-naphthol.
90%	With silica perchloric acid at 85℃; for 11h; Neat (no solvent);

83%	With nano-Fe₃O₄-bonded nicotinic acid-sulfonic acid chloride In neat (no solvent) at 80℃; for 0.116667h;	General procedure for solvent free synthesis of 1-carbamato-alkyl-2-naphthols General procedure: A mixture of 2-naphthol (2.0 mmol), benzyl carbamate (2.2 mmol), aromatic aldehyde (2.0 mmol) and Fe3O4 nicotinic acid sulfonic acid chloride nanoparticles(0.02 g) as a nanostructured magnetic catalyst was stirred magnetically at 80 °C in an oil bath for an appropriate time. The completion of the reaction was monitored by TLC. Hot ethyl acetate was added to reaction vessel in order to dissolve the reaction mixture. The catalyst was separated easily by an external magnet. After recrystallization, pure crystals of 1-carbamato-alkyl-2- naphtholderivatives were obtained. The products were identified by spectral and physical data. The recovered catalyst was washed with hot ethyl acetate for several times, and dried to reuse for another reaction. The recovered catalyst was used again for four times on the synthesis of 1-carbamato-alkyl-2-naphthol derivatives without asignificant decrease in the yield of products. The obtained products were identified by 1H NMR, 13C NMR and FT-IR analysis.
80%	With sulfamic acid-functionalised magnetic nanoparticles at 80℃; for 0.5h; neat (no solvent);

Reference： [1]Shaterian, Hamid Reza; Hosseinian, Asghar; Ghashang, Majid [Tetrahedron Letters, 2008, vol. 49, # 40, p. 5804 - 5806]
[2]Zare, Abdolkarim; Merajoddin, Maria; Moosavi-Zare, Ahmad Reza; Zarei, Mahmoud; Beyzavi, M. Hassan; Zolfigol, Mohammad Ali [Research on Chemical Intermediates, 2016, vol. 42, # 3, p. 2365 - 2378]
[3]Location in patent: experimental part Shaterian, Hamid Reza; Hosseinian, Asghar; Ghashang, Majid [Synthetic Communications, 2009, vol. 39, # 14, p. 2560 - 2574]
[4]Khazaei, Ardeshir; Tavasoli, Mahsa; Moosavi-Zare, Ahmad Reza [Research on Chemical Intermediates, 2018, vol. 44, # 10, p. 5893 - 5910]
[5]Location in patent: scheme or table Yarahmadi, Hossein; Shaterian, Hamid Reza [Journal of Chemical Research, 2012, vol. 36, # 1, p. 52 - 55]

53
[ 2628-16-2 ]
[ 621-84-1 ]
[ 851714-32-4 ]

Yield	Reaction Conditions	Operation in experiment
73%	Stage #1: O-benzyl carbamate With potassium hydroxide; tert-butylhypochlorite In water; acetonitrile at 0 - 4℃; for 0.166667h; Stage #2: p-acetoxystyrene With potassium osmate(VI); potassium phosphate buffer; hydroquinidine (anthraquinone-1,4-diyl) diether In water; acetonitrile at 21 - 23℃; for 0.833333h;	[000225] General procedure for asymmetric aminohydroxylation of styrenes [000226] As described for the synthesis of [ (S)-2-hydroxy-2- (4-acetoxy-phenyl)- ethyl]-carbamic acid benzyl ester (5): [000227] In a 1000 mL round bottom three-neck flask, under an atmosphere of N2, benzyl carbamate was dissolved (2.849 g, 18.6 mmol) in 120 mL of acetonitrile. The solution was cooled down in a water-ice bath (0-4 °C) and under efficient stirring a cold solution of potassium hydroxide (0.758 g KOH in 80 mL of water) was added. The solution was stirred 2 minutes, then a cold solution of tert-butyl hypochlorite (1.344 g, 12.4 mmol) in 20 mL of acetonitrile was added; the solution was then stirred for 10 min. A solution of potassium osmate (88.9 mg, 0.241 mmol) in 20 mL of cold H20 was then added. After 2 min a solution of DHQ2AQN (280.0 mg, 0.326 mmol) in 20 mL of CH3CN was added, then a solution of 100 mL of cold acetonitrile was added and stirred for 3 min. Potassium phosphate buffer (240 mL, pH=7.57) was added, the cooling bath removed, and the solution allowed to stir for 5 min (the solution turned light green immediately). At this point the pH was checked and if necessary adjusted to pH=7. 650. 02 by addition of a monobasic sodium phosphate solution. A solution of styrene (1.005 mg, 6.2 mmol) in 40 mL of acetonitrile was then added in one portion. The reaction mixture was vigorously stirred at room temperature (21-23 °C). After 45-50 min the solution turns yellow, indicating completion (as verified by TLC disappearance of starting material). [000228] The reaction mixture was cooled to 0-4 °C in an ice bath and 2.04 g of sodium sulfite in 20 mL of water was added. After 15 min of stirring the organic layer was separated and the aqueous layer was extracted with ethyl acetate (3x150 mL). The combined organic extracts were washed with water (2x100 mL) and brine (3x100 mL), and dried over anhydrous magnesium sulfate. Solvent evaporation resulted 4.186 g of amorphous crystals, which was subjected to flash column chromatography (silica gel, 2: 1=Hexane : EtOAc) to yield 1.410 g of 5 (71% isolated yield, 73% ee) as colorless crystals. The material was crystallized from EtOAc/hexane mixture (to a boiling suspension in hexanes (130 mL) EtOAc was added in portions until clear solution is obtained (37 mL) ) to afford 0.380 g of colorless plate-like crystals (20% ee) after filtration. The solution obtained after filtration was evaporated and recrystallized as described above second time to yield 0. 882 g (43% of theoretical yield) of needle-like crystals (>99% ee), 0.106 g of material remained in solution (>97% ee). [000229] SFC (125psi C02, 12%, 3mL/min MeOH, Chiracel OD) 6.951 min (R), 7.384 (S) [a] 25D=29. 64901 (c=. 895, CHCI3, [a] 25D=-16. 7102 in MeOH at c=. 31) (enantiomer, obtained with DHQD2AQN ligand, resulted [a] 25D=-29. 6437 (c=. 98, CHCI3))

Reference： [1]Current Patent Assignee: UNIVERSITY OF ILLINOIS (SYSTEM) - WO2005/44191, 2005, A2 Location in patent: Page/Page column 29; 30

54
[ 7315-32-4 ]
[ 621-84-1 ]
[ 1080596-31-1 ]

Reference： [1]Journal of Organic Chemistry,2008,vol. 73,p. 8973 - 8978

55
[ 621-84-1 ]
[ 3101-60-8 ]
[ 250778-94-0 ]
[ 1173884-62-2 ]

Reference： [1]European Journal of Organic Chemistry,2009,p. 2863 - 2871
[2]Journal of Organic Chemistry,2013,vol. 78,p. 9076 - 9084

56
[ 621-84-1 ]
[ 1007-03-0 ]
[ 1108697-84-2 ]

Reference： [1]Chemistry - A European Journal,2008,vol. 14,p. 10486 - 10495

57
[ 621-84-1 ]
[ 62005-48-5 ]
[ 1262142-18-6 ]

Reference： [1]Journal of Organic Chemistry,2011,vol. 76,p. 704 - 707

58
[ 101-02-0 ]
[ 621-84-1 ]
[ 7044-92-0 ]
[ 1300663-93-7 ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,2011,vol. 186,p. 983 - 988

59
[ 101-02-0 ]
[ 621-84-1 ]
[ 7310-97-6 ]
[ 1300663-98-2 ]

Reference： [1]Phosphorus, Sulfur and Silicon and the Related Elements,2011,vol. 186,p. 983 - 988

60
[ 621-84-1 ]
[ 66-99-9 ]
[ 762-72-1 ]
N-benzyloxycarbonyl-1-(2-naphthyl)but-3-enylamine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With magnesium bis(trifluoromethane solfonyl)imide In ethanol at 20℃; for 0.25h;
80%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
80%	Stage #1: O-benzyl carbamate; β-naphthaldehyde With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 2.5h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

65%

With iodine In acetonitrile at 20℃;

Reference： [1]Location in patent: experimental part Wang, Hongshe; Zhao, Weixing [Journal of Chemical Research, 2011, vol. 35, # 5, p. 310 - 312] Location in patent: experimental part Wang, Hongshe; Zeng, June [Bulletin of the Korean Chemical Society, 2011, vol. 32, # 7, p. 2203 - 2206]
[2]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[3]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[4]Borah, Arun Jyoti; Phukan, Prodeep [Journal of Chemical Sciences, 2013, vol. 125, # 6, p. 1503 - 1510]

61
[ 593-08-8 ]
[ 621-84-1 ]
[ 762-72-1 ]
[ 1356668-13-7 ]

Reference： [1]Chemical Communications,2012,vol. 48,p. 1820 - 1822

62
[ 3056-18-6 ]
[ 621-84-1 ]
[ 1360804-49-4 ]

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 1358 - 1362

63
[ 621-84-1 ]
[ 496-11-7 ]
[ 1294500-20-1 ]

Yield	Reaction Conditions	Operation in experiment
78%	With 2,3-dicyano-5,6-dichloro-p-benzoquinone In nitromethane at 80℃; for 4h;	General experimental procedure General procedure: To a solution of amide 2 (0.3 mmol), allylic or benzylic sp3 C-H compound 1 (1.5 mmol) in CH3NO2 (3 mL) was added DDQ (0.36 mmol). The resulting mixture was heated at 80 °C while stirring for indicated time. After completion of the reaction as evidenced by TLC, the reaction mixture was cooled to room temperature and filtered. Filtrate was diluted with water (10 mL) and extracted into ethyl acetate (3 × 10 mL). The combined organic layer was washed with saturated NaHCO3 solution, dried over anhydrous Na2SO4 and concentrated under reduced pressure to give crude residue, which was purified on silica gel column chromatography using hexane and ethyl acetate as the eluent to give the pure product. All products were characterized by 1H, 13C, IR, and mass spectral data.

Reference： [1]Location in patent: experimental part Ramesh; Ramulu; Mukkanti; Venkateswarlu [Tetrahedron Letters, 2012, vol. 53, # 23, p. 2904 - 2908]

64
[ 621-84-1 ]
[ 1125-88-8 ]
[ 39896-97-4 ]

Yield	Reaction Conditions	Operation in experiment
85%	With triethylsilane; perrhenic acid anhydride In dichloromethane at 20℃; for 3h; chemoselective reaction;

Reference： [1]Das, Braja Gopal; Ghorai, Prasanta [Chemical Communications, 2012, vol. 48, # 66, p. 8276 - 8278]

65
[ 621-84-1 ]
[ 127657-97-0 ]
[ 1416804-67-5 ]

Reference： [1]Russian Journal of General Chemistry,2012,vol. 82,p. 1882 - 1885
Zh. Obshch. Khim.,2012,vol. 82,p. 1919 - 1922

66
[ 24686-78-0 ]
[ 621-84-1 ]
[ 80213-01-0 ]
[ 780787-41-9 ]

Reference： [1]Organic and Biomolecular Chemistry,2013,vol. 11,p. 4379 - 4382

67
[ 1072-72-6 ]
[ 621-84-1 ]
[ 29683-23-6 ]
[ 402927-98-4 ]

Reference： [1]Organic and Biomolecular Chemistry,2013,vol. 11,p. 4379 - 4382

68
[ 924-44-7 ]
[ 621-84-1 ]
[ 104473-51-0 ]

Yield	Reaction Conditions	Operation in experiment
100%	In ethyl acetate at 60℃; for 24h;	1.2 Method two: through the step-by-step synthesis approach, first by CbzNH2 and glyoxylate condensation, getN, O hemiacetal, and then protect the hydroxyl group, and then get N, O acetal raw material, the specific method includes the following process steps:CbzNH2 (benzyl carbamate) and ethyl glyoxylate were mixed in a molar ratio of 1: 1.3 and reacted in ethyl acetate at 60 ° C for 1 day. The solvent was removed by rotary evaporation to give a solid N, O hemiacetal. An additional 5 molar equivalents (ie, five times the molar amount of CbzNH2) of acetic anhydride and 1 molar% of pyridine are added and the reaction is allowed to proceed at 25 ° C for 1 day to remove unreacted acetic anhydride to give branched Cbz protected amine groups N, O-acetal compounds, the specific reaction equation shown in Figure 3.
97%	With acetic acid In ethyl acetate; toluene at 60℃; for 14h; Inert atmosphere;
81%	With acetic acid In ethyl acetate at 60℃; for 14h; Inert atmosphere;

81%	With diphenyl hydrogen phosphate In diethyl ether; toluene at 20℃; for 20h;	General Procedure for the Synthesis of the Carboniolamide General procedure: To a reaction vial charged with amide (1.0mmol), glyoxylate (1.0 mmol), and diphenyl hydrogen phosphate (25.0 mg, 0.1 mmol) was added Et2O (4 mL). Then the sealed reaction mixture was stirred at r.t. for the specified time. The obtained slurry was then filtered, and the precipitate was washed with a minimum amount of cold Et2O to give the compound as a white powder.
81%	With diphenyl hydrogen phosphate In diethyl ether; toluene at 20℃; for 20h; Sealed tube;	General Procedure for the Synthesis of the Carboniolamide: General procedure: To a reaction vial charged with amide (1.0mmol), glyoxylate (1.0 mmol), and diphenyl hydrogenphosphate (25.0 mg, 0.1 mmol) was added Et2O (4 mL).Then the sealed reaction mixture was stirred at r.t. for the specified time. The obtained slurry was then filtered, and the precipitate was washed with a minimum amount of cold Et2O to give the compound as a white powder.
71%	With acetic acid In ethyl acetate; toluene Reflux;
	With acetic acid In ethyl acetate; toluene for 12h; Reflux;

Reference： [1]Current Patent Assignee: CHINESE ACADEMY OF SCIENCES; Institute of Chemistry (in: CAS) - CN107325025, 2017, A Location in patent: Paragraph 0093; 0096; 0097
[2]You, Yang'en; Zhang, Long; Cui, Linfeng; Mi, Xueling; Luo, Sanzhong [Angewandte Chemie - International Edition, 2017, vol. 56, # 44, p. 13814 - 13818][Angew. Chem., 2017, vol. 129, # 44, p. 14002 - 14006,5]
[3]Roche, Stephane P.; Samanta, Shyam S.; Gosselin, Marine M. J. [Chemical Communications, 2014, vol. 50, # 20, p. 2632 - 2634]
[4]Zhang, Yi; Dai, Yuchi; Li, Guigen; Cheng, Xu [Synlett, 2014, vol. 25, # 18, p. 2644 - 2648]
[5]Zhang, Yi; Dai, Yuchi; Li, Guigen; Cheng, Xu [Synlett, 2014, vol. 25, # 16]
[6]Wasa, Masayuki; Liu, Richard Y.; Roche, Stéphane P.; Jacobsen, Eric N. [Journal of the American Chemical Society, 2014, vol. 136, # 37, p. 12872 - 12875]
[7]Bendelsmith, Andrew J.; Kim, Seohyun Chris; Wasa, Masayuki; Roche, Stéphane P.; Jacobsen, Eric N. [Journal of the American Chemical Society, 2019, vol. 141, # 29, p. 11414 - 11419]

69
[ 621-84-1 ]
[ 131818-17-2 ]
[ 220741-56-0 ]

Reference： [1]Green Chemistry,2014,vol. 16,p. 1480 - 1488

70
[ 621-84-1 ]
[ 7745-93-9 ]
[ 875118-52-8 ]

Yield	Reaction Conditions	Operation in experiment
99%	With di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine; bis(η3-allyl-μ-chloropalladium(II)); triisopropylsilanol; potassium hydroxide In water at 50℃; for 24h; Inert atmosphere; Green chemistry;

Reference： [1]Isley, Nicholas A.; Dobarco, Sebastian; Lipshutz, Bruce H. [Green Chemistry, 2014, vol. 16, # 3, p. 1480 - 1488]

71
[ 621-84-1 ]
[ 16939-57-4 ]
[ 920285-74-1 ]

Yield	Reaction Conditions	Operation in experiment
74%	With [2,2]bipyridinyl; copper(II) trifluoromethanesulfonate In 1,4-dioxane at 75℃; for 5h; regioselective reaction;	Synthesis of E-4-Phenyl-3-buten-2-amine N-Benzyloxycarbonyl Ester In a round bottom flask (250 ml) equipped with amagnetic stir bar and reflux condenser wereplaced copper trifluoromethanesulfonate (297 mg, 0.85 mmol), 2,2-bipyridine (102 mg,0.67 mmol) and 1,4-dioxane (60 ml). Benzyl carbamate (5.0 g, 33 mmol) and 1-phenyl-1,3-butadiene (5.2 g, 40 mmol) were added to the flask and the mixture was stirred at 75Cfor 5 h. Upon completion, the reaction mixture was diluted with ethyl acetate (40 ml) andwashed with 1M aq. NaHCO3 (40 ml). The layers were separated and the organic layer wasdried over Na2SO4, concentrated under vacuum, and purified by column chromatography(3:1 hexanes/EtOAc) to provide the product as a crystalline white solid (6.9 g, 74%), mp.82-84C (lit.19 89-90C); Rf = 0.3 (hexanes/EtOAc, 4:1); IR (cm-1): 3320, 3026, 2982,2939, 2898, 1950, 1876, 1681; 1H NMR (400 MHz): δ 7.39-7.28 (10H, m), 6.56 (1H, d,J = 16.0), 6.22 (1H, dd, J = 6.0, 16.0), 5.15 (2H, s) 4.84 (1H, br s), 4.51-4.55 (1H, br m),1.38 (3H, d, J = 6.8); 13C NMR (100 MHz): δ 155.6, 136.7, 136.6, 131.2, 129.6, 128.6,128.2, 127.7, 127.6, 126.5, 126.4, 66.8, 48.5, 21.1; m/z (EI): 281 (M+, 10%), 222 (30%),190 (50%), 129 (60%), 91 (100%), 65 (15%), 42 (12%). The NMR data are in accordancewith literature values

Reference： [1]Ventura, Wellington Martins; Taylor, Jason Guy [Organic Preparations and Procedures International, 2014, vol. 46, # 4, p. 381 - 385]

72
[ 4397-53-9 ]
[ 621-84-1 ]
[ 762-72-1 ]
[ 1621185-18-9 ]

Yield	Reaction Conditions	Operation in experiment
90%	With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h;	4.1 General procedure for synthesis of secondary or tertiary N-homoallylic carbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile (1 mL) was added 30 mol% or 40 mol% HBF4·OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5mmol or 2.0mmol) and dry acetonitrile (1mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10mL) solution was added to the reaction mixture and extracted with ethyl acetate (3× 10 mL). The organic layer was washed with brine (1× 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallylic carbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma, 4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.
90%	Stage #1: p-benzyloxybenzaldehyde; O-benzyl carbamate With tetrafluoroboric acid diethyl ether In acetonitrile at 20℃; for 0.166667h; Stage #2: allyl-trimethyl-silane In acetonitrile at 20℃; for 2h;	4.1. General procedure for synthesis of secondary or tertiary Nhomoallyliccarbamates General procedure: To a solution of an aldehyde 1 or ketone 5 (1 mmol), benzylcarbamate 2 (1.2 mmol or 1.5 mmol) in dry acetonitrile(1 mL) was added 30 mol% or 40 mol% HBF4*OEt2 [20] and the mixture was stirred at room temperature for 10 min followed by subsequent addition of allyltrimethylsilane 3 (1.5 mmol or2.0 mmol) and dry acetonitrile (1 mL). After completion of the reaction (TLC, specified time) saturated aq. NaHCO3 (10 mL)solution was added to the reaction mixture and extracted with ethyl acetate (3 10 mL). The organic layer was washed with brine (1 10 mL) and dried over anhydrous sodium sulfate. The organic layer was concentrated under rotary evaporator and column chromatographed on silica gel (100-200 mesh) using 2:8 ethyl acetate-hexane as the eluent to get pure the N-homoallyliccarbamates. Compounds 4aa, 4ba, 4ca, 4fa, 4ha, 4ja, 4ka, 4ma,4na, 6ba and 6ca are known in the literature and they have been confirmed by comparison of their IR, 1H NMR and 13C NMR data with those reported data (Refs. [1d,3c,10]). Full characteristic data of all new compounds 4da, 4ea, 4ga, 4ia, 4la and 6aa are as follows.

Reference： [1]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]
[2]Baishya, Gakul; Hazarika, Nabajyoti; Sarmah, Barnali [Journal of Fluorine Chemistry, 2014, vol. 166, p. 1 - 7]

73
[ 2768-56-1 ]
[ 621-84-1 ]
C₁₄H₁₈N₂O₄ [ No CAS ]

Reference： [1]Angewandte Chemie - International Edition,2014,vol. 53,p. 6501 - 6505

74
[ 3598-60-5 ]
[ 621-84-1 ]
[ 159395-40-1 ]
(2,4-bis(ethoxycarbonyl)butyl)(1-(benzyloxycarbonylamino)-4-(phthalylamino)butyl)phosphinic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
33%	In acetic anhydride; acetyl chloride for 30h;	2,4-Bis(ethoxycarbonyl)butyl-1-(benzyloxycarbonylamino)-4-(phthalylamino)butylphosphinic acid(7). 5.7 g (26 mmol) of 4-(phthalyl)aminobutyraldehyde 6 was slowly added to a stirred solution of 7.0 g (26 mmol) of compound 3c and 4.0 g (26 mmol) of benzylcarbamate in 40 mL of a 1:1 acetic anhydride-acetyl chloride mixture. The reaction mixture was stirred during 30 h, concentrated via co-evaporation with toluene, poured into 50 mL of ice water, and evaporated. The residue was dissolved in 30 mL of chloroform, washed with water (2 × 10 mL), and evaporated in a vacuum. The residue was crystallized from petroleum ether and recrystallized from diethylether. Yield 5.3 g (33 %), white powder, mp 81-83°C, Rf 0.23 (CHCl3 : MeOH : AcOH = 10 : 2 : 1). 1H NMR spectrum (CDCl3), δ, ppm: 1.21 m (6H, CH3), 1.50-2.00 m (1H, PCH2; 4, CH2CH2CHN; 2, CH2CH2CO), 2.00-2.40 m (1H, PCH2; 2, CH2CO), 2.80 m (1H, PCH2CH), 3.68 m (2H, NCH2), 3.95 m (1H, CHN), 4.08 q (4H, CH2O, 2JH 6.8 Hz), 5.03 m (2H, CH2Ph), 5.82 d.d (1H, NH, 3JH 9.8, 3JH 4.7 Hz), 7.2-7.4 m (5H, C6H5), 7.55-7.70 m (2H, Phth), 7.70-7.90 m (2H, Phth). 13C NMR spectrum (CDCl3), δ,ppm (hereafter the asterisk marks the signals of the other diastereomer): 14.1, 14.2, 25.1 d (3JP 20.5 Hz), 25.2* d (3JP 19.8 Hz), 27.8, 28.6, 29.6, 31.3, 37.4, 38.2, 49.4 d (1JP 105.0 Hz), 50.0* d (1JP 105.0 Hz), 60.5, 61.0, 67.2, 123.3, 128.2, 128.5, 132.0, 134.0, 136.3, 156.4 d (3JP 4.4 Hz), 168.5, 172.7, 173.9 (3JP7.7 Hz). 31P NMR spectrum (CDCl3), δP, ppm: 54.1, 54.4*.

Reference： [1]Dmitriev; Ragulin [Russian Journal of General Chemistry, 2015, vol. 85, # 9, p. 2091 - 2098][Zh. Obshch. Khim., 2015, vol. 85, # 9, p. 1511 - 1519,9]

75
[ 621-84-1 ]
[ 66-39-7 ]
[ 22979-35-7 ]
(2R*,3R*)-methyl 2-(((benzyloxy)carbonyl)amino)-3-hydroxy-3-(4-(methylsulfonyl)phenyl)-2-phenylpropanoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With indium(III) chloride; Rh2(OAc)4; In 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran; at 20℃; for 1h;Molecular sieve;	General procedure: To a stirred mixture of Rh2(OAc)4 (1 mol%), InCl3 (15 mol%), carbamate 1 (0.20mmol), aldehyde 2 (0.24mmol), and 4-MS (100mg) in DCM (1.5mL) was added diazo compound 3 (0.38mmol) in DCM (1mL) in portions at room temperature. After the addition of diazo compound was complete, the reaction mixture was stirred for 1h. Then, the reaction mixture was filtered and concentrated under reduced pressure. The crude product was subjected to 1H NMR analysis for the determination of diastereoselectivity. The crude product was purified by column chromatography on silica gel (eluent: EtOAc/light petroleum=1:20-1:10) to give the corresponding pure products 4.

Reference： [1]Tetrahedron,2016,vol. 72,p. 579 - 583

76
[ 28001-33-4 ]
[ 107-86-8 ]
[ 621-84-1 ]
benzyl 2-cyclopropyl-6-methyl-1,3-dioxo-2,3,3a,4,7,7a-hexahydro-1H-isoindol-4-ylcarbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
72.8%	With toluene-4-sulfonic acid In toluene at 120℃;	2 Step 2: Preparation of benzyl benzyl 2-cyclopropyl-6-methyl-l,3-dioxo-2,3,3a,4,7,7a- hexahydro-lH-isoindol-4-ylcarbamate. Step 2: Preparation of benzyl benzyl 2-cyclopropyl-6-methyl-l,3-dioxo-2,3,3a,4,7,7a- hexahydro-lH-isoindol-4-ylcarbamate. To a stirred solution of l-cyclopropyl-lH-pyrrole-2,5-dione (8.0 g, 1.0 eq.), 3-methylbut-2-enal (9.8 g, 2.0 eq.) and benzyl carbamate (8.8 g, 1.0 eq.) in toluene (100 mL) at rt was added PTSA (443 mg, 0.04 eq.) and the resulting mixture was heated to 120 °C. The reaction mixture was extracted with ethyl acetate (2 x 200 mL) and washed with water (1 x 200 mL), dried over anhydrous Na2S04, filtered, rotary evaporated and dried under vacuum to afford crude product. The crude product was purified by column chromatography (silica gel, eluent EtOAc/ Hexane 20:80) to afford 15 g (72.8%, LC-MS 35%) of benzyl benzyl 2-cyclopropyl-6-methyl-l,3-dioxo- 2,3,3a,4,7,7a-hexahydro-lH-isoindol-4-ylcarbamate as a colorless viscous liquid.

Reference： [1]Current Patent Assignee: AGENCY FOR SCIENCE, TECHNOLOGY AND RESEARCH - WO2015/187094, 2015, A1 Location in patent: Paragraph 0218

77
[ 621-84-1 ]
[ 3355-28-0 ]
benzyl di(but-2-yn-1-yl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
79%	Stage #1: 1-Bromo-2-butyne With sodium hydride In N,N-dimethyl-formamide at 0℃; for 0.25h; Inert atmosphere; Stage #2: O-benzyl carbamate In N,N-dimethyl-formamide at 0 - 20℃; for 3h; Inert atmosphere;	1 Benzyl di(but-2-yn-1-yl)carbamate Benzyl di(but-2-yn-1-yl)carbamate (0088) To an ice-cooled solution of 1 -bromobut-2-yne (581 g, 2.2 eq) in DMF (3.5L) was added NaH (60%, 199 g, 2.5 eq) carefully and the mixture was stirred at 0°C under N2 atmosphere for 15 min. Then a solution of benzyl carbamate (300 g, 1 .985 mol, 1 eq) in DMF (500ml_) was added dropwise at 0°C for 1 h and the resulting mixture was allowed to warm to ambient temperature for 2h. After being quenched cautiously with H20, the reaction was extracted with ether (x2). The organic layer was washed with H20 (x3), brine, dried over anhydrous Na2S04, filtered, and concentrated. The residue was purified by column chromatography (silica gel, 0 - 5% EtOAc in hexane) to afford the title compound (398 g, 79%). NMR (400 MHz, CDCI3) δ 7.41 - 7.27 (m, 5H), 5.17 (s, 2H), 4.18 (s, 4H), 1 .81 (t, J = 2.3 Hz, 6H). LC-MS (ESI+): m/z (M+H) =256.3
58%	With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 0.666667h; Cooling with ice;	1.3 Ster 3: Benzyl di(but-2-yn- 1 -yl)carbamate Ster 3: Benzyl di(but-2-yn- 1 -yl)carbamate/-OPhTo a suspension of NaH (27.8 mmol, 1 .11 g, 60% dispersion) in DMF (100 mL) was added 1-bromobut-2-yne (27.1 mmol, 2.375 mL). The reaction mixture was cooled in an ice bath and a solution of benzyl carbamate (13.23 mmol, 2.0 g) in DMF (10 mL) was added dropwise over 25 mm. The ice bath was removed and the reaction mixture stirred at ambient temperature. After 15 mm, the reaction mixture was poured slowly over ice. The mixture was extracted with ether (3x1 00 mL) and the combined organic layers were washed with H20 (4 x 100 mL), brine, dried over Na2SO4 and concentrated in vacuo. The crude material was purified via silica gel chromatography (0-100% EtOAc-hexanes) to afford the title compound as a yellow oil (1 .94 g, 58% yield). 1H NMR (400 MHz, ODd3) 57.39-7.30 (m, 4H), 5.17 (s, 2H), 4.18 (s, 4H), 1.81 (s, 6H). LCMS (ES+)(m/z): 256.8 (M+H).

Reference： [1]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2017/93930, 2017, A1 Location in patent: Page/Page column 8
[2]Current Patent Assignee: GLAXOSMITHKLINE PLC - WO2016/5878, 2016, A1 Location in patent: Page/Page column 8; 9

78
[ 2591-98-2 ]
[ 621-84-1 ]
[ 873-55-2 ]
C₂₄H₂₂N₂O₄S [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2016,vol. 138,p. 14234 - 14237

79
[ 621-84-1 ]
[ 625-95-6 ]
[ 108716-18-3 ]

Yield	Reaction Conditions	Operation in experiment
80%	With copper(l) iodide; ethylenediamine; sodium t-butanolate In toluene at 100℃; for 6h;	2.2 General Procedure for the Synthesis of Alkyl Aryl Carbamates General procedure: CuI (10mol%) and EDA (10mol%) were added to a mixtureof O-alkyl carbamate (1mmol), NaOtBu (1.5mmol) and aryl halide (1mmol) in 2mL toluene and the mixture wasstirred for the appropriate time, which was determined byTLC monitoring, at 100°C. After completion of the reaction,the catalyst was removed by filtration and 20mL H2Owas added to the filtrate. The resultant mixture was extractedwith CHCl3.Then the organic phase was washed with water(2 × 10mL) and dried over anhydrous Na2SO4.After evaporationof CHCl3under reduced pressure, the correspondingcrude product was purified by flash chromatography to givethe desired pure cross-coupling product in good to excellentyield. In the case of using arylboronic acids as couplingpartners, Cu(OAc)2 was employed instead of CuI.

Reference： [1]Sardarian, Ali Reza; DindarlooInaloo, Iman; Zangiabadi, Milad [Catalysis Letters, 2018, vol. 148, # 2, p. 642 - 652]

80
[ 10486-61-0 ]
[ 621-84-1 ]
benzyl thiophen-3-ylcarbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With copper(l) iodide; ethylenediamine; sodium t-butanolate In toluene at 100℃; for 5.5h;	2.2 General Procedure for the Synthesis of Alkyl Aryl Carbamates General procedure: CuI (10mol%) and EDA (10mol%) were added to a mixtureof O-alkyl carbamate (1mmol), NaOtBu (1.5mmol) and aryl halide (1mmol) in 2mL toluene and the mixture wasstirred for the appropriate time, which was determined byTLC monitoring, at 100°C. After completion of the reaction,the catalyst was removed by filtration and 20mL H2Owas added to the filtrate. The resultant mixture was extractedwith CHCl3.Then the organic phase was washed with water(2 × 10mL) and dried over anhydrous Na2SO4.After evaporationof CHCl3under reduced pressure, the correspondingcrude product was purified by flash chromatography to givethe desired pure cross-coupling product in good to excellentyield. In the case of using arylboronic acids as couplingpartners, Cu(OAc)2 was employed instead of CuI.

Reference： [1]Sardarian, Ali Reza; DindarlooInaloo, Iman; Zangiabadi, Milad [Catalysis Letters, 2018, vol. 148, # 2, p. 642 - 652]

81
[ 621-84-1 ]
[ 3289-28-9 ]
C₁₈H₂₃NO₅ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
86%	With trifluorormethanesulfonic acid; (S)-N<SUP>1</SUP>,N<SUP>1</SUP>,3,3- tetramethylbutane-1,2-diamine; 3-nitrobenzoic acid In dichloromethane at 60℃; for 48h;	3 Embodiment 3, In accordance with the following reaction equation as follows preparation:The cyclohexyl acid ethyl ester (50 mmol) with N, O - acetal (75 mmol) added into the reactor, and then the type 5 - 1 indicated by the chiral primary uncle diamine organic small molecule catalyst (2.5 mmol) for 1 ml dichloromethane dissolved, under low warm ice-bath drips into three fluorine armor sulfonic acid (2.5 mmol), evaporate dichloromethane then this catalyst in the reactor, and finally adding m-nitrobenzoic acid (12.5 mmol), heating to 60 °C, stirring 2 days after the completion of the reaction, column chromatography separation to obtain the target product β - amino acid ester 86%,>99% ee.

Reference： [1]Current Patent Assignee: Institute of Chemistry (in: CAS); CHINESE ACADEMY OF SCIENCES - CN107382783, 2017, A Location in patent: Paragraph 0086-0089

82
[ 101-02-0 ]
[ 621-84-1 ]
[ 197638-83-8 ]
tert-butyl 4-(4-((((benzyloxy)carbonyl)amino)(diphenoxyphosphoryl)methyl)phenyl)piperazine-1-carboxylate [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2019,vol. 62,p. 774 - 797

83
[ 101-02-0 ]
[ 621-84-1 ]
[ 197638-83-8 ]
benzyl ((diphenoxyphosphoryl)(4-(piperazin-1-yl)phenyl)methyl)carbamate 2,2,2-trifluoroacetate [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2019,vol. 62,p. 774 - 797

84
[ 101-02-0 ]
[ 10035-16-2 ]
[ 621-84-1 ]
benzyl (benzofuran-5-yl(diphenoxyphosphoryl)methyl)carbamate [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2019,vol. 62,p. 774 - 797

85
[ 101-02-0 ]
[ 54221-96-4 ]
[ 621-84-1 ]
benzyl ((diphenoxyphosphoryl)(6-methoxypyridin-2-yl)methyl)carbamate [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2019,vol. 62,p. 774 - 797

86
[ 101-02-0 ]
[ 621-84-1 ]
[ 59935-39-6 ]
benzyl ((4-(dimethylamino)-3-nitrophenyl)(diphenoxyphosphoryl)methyl)carbamate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
55%	With copper(II) bis(trifluoromethanesulfonate) In dichloromethane at 20℃; for 16h;

Reference： [1]Moreno-Cinos, Carlos; Sassetti, Elisa; Salado, Irene G.; Witt, Gesa; Benramdane, Siham; Reinhardt, Laura; Cruz, Cristina D.; Joossens, Jurgen; Van Der Veken, Pieter; Brötz-Oesterhelt, Heike; Tammela, Päivi; Winterhalter, Mathias; Gribbon, Philip; Windshügel, Björn; Augustyns, Koen [Journal of Medicinal Chemistry, 2019, vol. 62, # 2, p. 774 - 797]

87
[ 20859-02-3 ]
[ 621-84-1 ]
[ 62965-10-0 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In dichloromethane; at 0℃;	General procedure: The reaction conditions of b are: the compound of formula I: acid chloride: base A is added to the solvent A in a molar ratio of 1: 1 to 2: 2 to 10, and the reaction is carried out at 0 degrees with stirring; the base A is triethylamine, the solvent A is dichloromethane,

Reference： [1]Patent: CN109970713,2019,A .Location in patent: Paragraph 0073

88
[ 13795-24-9 ]
[ 621-84-1 ]

Reference： [1]Journal of Medicinal Chemistry,2020,vol. 63,p. 4685 - 4700

Purity	Size	Price	VIP Price	USA Stock *0-1 Day	Global Stock *5-7 Days	Quantity
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CAS No. :	621-84-1	MDL No. :	MFCD00007965
Formula :	C₈H₉NO₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	PUJDIJCNWFYVJX-UHFFFAOYSA-N
M.W :	151.16	Pubchem ID :	12136
Synonyms :

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.12
Num. rotatable bonds :	3
Num. H-bond acceptors :	2.0
Num. H-bond donors :	1.0
Molar Refractivity :	40.6
TPSA :	52.32 Å²

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.37 cm/s

Log Po/w (iLOGP) :	1.58
Log Po/w (XLOGP3) :	1.2
Log Po/w (WLOGP) :	1.13
Log Po/w (MLOGP) :	1.19
Log Po/w (SILICOS-IT) :	0.84
Consensus Log Po/w :	1.19

[ CAS No. 621-84-1 ] {[proInfo.proName]}

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[ 621-84-1 ] Synthesis Path-Upstream 1~9

[ 621-84-1 ] Synthesis Path-Downstream 1~88

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Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Log S (ESOL) :	-1.74
Solubility :	2.76 mg/ml ; 0.0182 mol/l
Class :	Very soluble
Log S (Ali) :	-1.9
Solubility :	1.92 mg/ml ; 0.0127 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-2.11
Solubility :	1.16 mg/ml ; 0.00769 mol/l
Class :	Soluble

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.43

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P280-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302-H315-H319-H332-H335	Packing Group:	N/A
GHS Pictogram:

Yield	Reaction Conditions	Operation in experiment
87%	at 120℃; for 2 h;	To a 250 ml. flask equipped mechanical stirring, was added 2-oxoacetic acid hydrate (9.2 g,0.1 mol), benzyl carbamate (15.1 g, 0.1 mol) and 1H-benzo[dj[1,2,3jtriazole (9.2 g, 0.1 mol), and toluene (300 mL). The resulting solution was stirred for 2 h at 120 °C in an oil bath. The resulting mixture was filtered and the solid residue was washed with petroleum ether (3x), and dried in vacuo to give 2-(1H-benzo[dj[1,2,3jtriazol-1-yl)-2-(benzyloxycarbonylamino)aceticacid (28.6 g, 87percent) as a white solid that was used without further purification. ESI-MS m/z:327 [M+Hf
87%	at 120℃; for 2 h;	To a 250 mL flask equipped mechanical stirring, was added 2-oxoacetic acid hydrate (9.2 g, 0.1 mol), benzyl carbamate (15.1 g, 0.1 mol) and 1H-benzo[d][1,2,3]triazole (9.2 g, 0.1 mol), and toluene (300 mL). The resulting solution was stirred for 2 h at 120° C. in an oil bath. The resulting mixture was filtered and the solid residue was washed with petroleum ether (3*), and dried in vacuo to give 2-(1H-benzo[d][1,2,3]triazol-1-yl)-2-(benzyloxycarbonylamino)acetic acid (28.6 g, 87percent) as a white solid that was used without further purification. ESI-MS m/z: 327 [M+H]⁺.
134.9 g	for 2 h; Reflux; Dean-Stark	A mixture of benzyl carbamate (82.1 g, 0.54 mol), glyoxylic acid monohydrate (50 g, 0.54 mol) and benzotriazole (64.7 g, 0.54 mol) in toluene (2.5 L) was heated at reflux with Dean and Stark water removal for 2 hours. A total of 23 mL of water was collected during the first hour before water evolution ceased. The mixture was allowed to cool to room temperature and the resulting solid filtered and washed with diethyl ether (200 mL). The damp filter cake was dried at 40 °C/50 mmHg overnight to give a cream coloured powder (134.9 g).

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P222	Do not allow contact with air.
P223	Keep away from any possible contact with water, because of violent reaction and possible flash fire.
P230	Keep wetted
P231	Handle under inert gas.
P232	Protect from moisture.
P233	Keep container tightly closed.
P234	Keep only in original container.
P235	Keep cool
P240	Ground/bond container and receiving equipment.
P241	Use explosion-proof electrical/ventilating/lighting/equipment.
P242	Use only non-sparking tools.
P243	Take precautionary measures against static discharge.
P244	Keep reduction valves free from grease and oil.
P250	Do not subject to grinding/shock/friction.
P251	Pressurized container: Do not pierce or burn, even after use.
P260	Do not breathe dust/fume/gas/mist/vapours/spray.
P261	Avoid breathing dust/fume/gas/mist/vapours/spray.
P262	Do not get in eyes, on skin, or on clothing.
P263	Avoid contact during pregnancy/while nursing.
P264	Wash hands thoroughly after handling.
P265	Wash skin thouroughly after handling.
P270	Do not eat, drink or smoke when using this product.
P271	Use only outdoors or in a well-ventilated area.
P272	Contaminated work clothing should not be allowed out of the workplace.
P273	Avoid release to the environment.
P280	Wear protective gloves/protective clothing/eye protection/face protection.
P281	Use personal protective equipment as required.
P282	Wear cold insulating gloves/face shield/eye protection.
P283	Wear fire/flame resistant/retardant clothing.
P284	Wear respiratory protection.
P285	In case of inadequate ventilation wear respiratory protection.
P231 + P232	Handle under inert gas. Protect from moisture.
P235 + P410	Keep cool. Protect from sunlight.
Response
Code	Phrase
P301	IF SWALLOWED:
P304	IF INHALED:
P305	IF IN EYES:
P306	IF ON CLOTHING:
P307	IF exposed:
P308	IF exposed or concerned:
P309	IF exposed or if you feel unwell:
P310	Immediately call a POISON CENTER or doctor/physician.
P311	Call a POISON CENTER or doctor/physician.
P312	Call a POISON CENTER or doctor/physician if you feel unwell.
P313	Get medical advice/attention.
P314	Get medical advice/attention if you feel unwell.
P315	Get immediate medical advice/attention.
P320
P302 + P352	IF ON SKIN: wash with plenty of soap and water.
P321
P322
P330	Rinse mouth.
P331	Do NOT induce vomiting.
P332	IF SKIN irritation occurs:
P333	If skin irritation or rash occurs:
P334	Immerse in cool water/wrap n wet bandages.
P335	Brush off loose particles from skin.
P336	Thaw frosted parts with lukewarm water. Do not rub affected area.
P337	If eye irritation persists:
P338	Remove contact lenses, if present and easy to do. Continue rinsing.
P340	Remove victim to fresh air and keep at rest in a position comfortable for breathing.
P341	If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P342	If experiencing respiratory symptoms:
P350	Gently wash with plenty of soap and water.
P351	Rinse cautiously with water for several minutes.
P352	Wash with plenty of soap and water.
P353	Rinse skin with water/shower.
P360	Rinse immediately contaminated clothing and skin with plenty of water before removing clothes.
P361	Remove/Take off immediately all contaminated clothing.
P362	Take off contaminated clothing and wash before reuse.
P363	Wash contaminated clothing before reuse.
P370	In case of fire:
P371	In case of major fire and large quantities:
P372	Explosion risk in case of fire.
P373	DO NOT fight fire when fire reaches explosives.
P374	Fight fire with normal precautions from a reasonable distance.
P376	Stop leak if safe to do so. Oxidising gases (section 2.4) 1
P377	Leaking gas fire: Do not extinguish, unless leak can be stopped safely.
P378
P380	Evacuate area.
P381	Eliminate all ignition sources if safe to do so.
P390	Absorb spillage to prevent material damage.
P391	Collect spillage. Hazardous to the aquatic environment
P301 + P310	IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician.
P301 + P312	IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell.
P301 + P330 + P331	IF SWALLOWED: Rinse mouth. Do NOT induce vomiting.
P302 + P334	IF ON SKIN: Immerse in cool water/wrap in wet bandages.
P302 + P350	IF ON SKIN: Gently wash with plenty of soap and water.
P303 + P361 + P353	IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower.
P304 + P312	IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell.
P304 + P340	IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing.
P304 + P341	IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing.
P305 + P351 + P338	IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing.
P306 + P360	IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes.
P307 + P311	IF exposed: call a POISON CENTER or doctor/physician.
P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling