[ CAS No. 30018-16-7 ] {[proInfo.proName]}

Name: 30018-16-7|(1-Ethoxy-1-oxopropan-2-yl)triphenylphosphonium bromide|97%
Brand: Ambeed
SKU: A111740
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2D 3D

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Quality Control of [ 30018-16-7 ]

COA NMR CNMR HPLC LC-MS

Related Doc. of [ 30018-16-7 ]

SDS Specification

Alternatived Products of [ 30018-16-7 ]

Product Details of [ 30018-16-7 ]

CAS No. :	30018-16-7	MDL No. :	MFCD00031605
Formula :	C₂₃H₂₄BrO₂P	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	RSYXORMKBUFAMS-UHFFFAOYSA-M
M.W :	443.31	Pubchem ID :	3084511
Synonyms :

Calculated chemistry of [ 30018-16-7 ]

Physicochemical Properties

Num. heavy atoms :	27
Num. arom. heavy atoms :	18
Fraction Csp3 :	0.17
Num. rotatable bonds :	7
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	120.45
TPSA :	39.89 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	Yes
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	Yes
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-4.55 cm/s

Lipophilicity

Log Po/w (iLOGP) :	-1.0
Log Po/w (XLOGP3) :	6.28
Log Po/w (WLOGP) :	0.94
Log Po/w (MLOGP) :	5.34
Log Po/w (SILICOS-IT) :	5.14
Consensus Log Po/w :	3.34

Druglikeness

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

Water Solubility

Log S (ESOL) :	-6.58
Solubility :	0.000118 mg/ml ; 0.000000265 mol/l
Class :	Poorly soluble
Log S (Ali) :	-6.91
Solubility :	0.0000551 mg/ml ; 0.000000124 mol/l
Class :	Poorly soluble
Log S (SILICOS-IT) :	-8.41
Solubility :	0.00000171 mg/ml ; 0.0000000039 mol/l
Class :	Poorly soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	2.0
Synthetic accessibility :	4.91

Safety of [ 30018-16-7 ]

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

Application In Synthesis of [ 30018-16-7 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 30018-16-7 ]
Downstream synthetic route of [ 30018-16-7 ]

[ 30018-16-7 ] Synthesis Path-Upstream 1~2

1
[ 603-35-0 ]
[ 535-11-5 ]
[ 30018-16-7 ]

Yield	Reaction Conditions	Operation in experiment
80.5%	at 20℃; for 24 h;	The 1g of triphenylphosphine were dissolved in 15mL ethyl acetate was added 2-bromopropionate ethyl ester0.55mL2-, the reaction was stirred at room temperature 24h, and gradually a large amount of white solid was suction filtered, rinsed with ethyl acetate to give 1.35 g of a white solid, yield rate of 80.5percent.
144 g	With potassium iodide In water; toluene at 20 - 75℃; for 15 h;	At 20-30°C,To a solution of triphenylphosphine (88 g) in toluene (the organic phase recovered in the first step of Example 3), an aqueous solution of potassium iodide (3 g) was added (the mother liquor from the first step of Example 3).Then alpha-bromo-propionic acid ethyl ester (60 g) is added,Reaction at 70-75 ° C for 15h;After the reaction is complete,Phase,Water cooling,Crystallization,Filtered to give the ethoxycarbonyl ethyl triphenylphosphonium bromide (144g);Organic phase recovery application,Aqueous mother liquor recovery application.

Reference： [1] European Journal of Organic Chemistry, 2016, vol. 2016, # 12, p. 2110 - 2114
[2] Chemistry - A European Journal, 2015, vol. 21, # 20, p. 7408 - 7412
[3] Tetrahedron, 2010, vol. 66, # 26, p. 4745 - 4759
[4] Journal of Organic Chemistry, 1984, vol. 49, # 22, p. 4293 - 4295
[5] Patent: CN103864753, 2016, B, . Location in patent: Paragraph 0087; 0110-0111
[6] Angewandte Chemie - International Edition, 2018, vol. 57, # 24, p. 7240 - 7244[7] Angew. Chem., 2018, # 130, p. 7360 - 7364,5
[8] Tetrahedron, 1991, vol. 47, # 18-19, p. 2991 - 2998
[9] Journal of Fluorine Chemistry, 1985, vol. 29, p. 363 - 384
[10] Organic and Biomolecular Chemistry, 2004, vol. 2, # 10, p. 1456 - 1470
[11] Organic Letters, 2010, vol. 12, # 2, p. 240 - 243
[12] Advanced Synthesis and Catalysis, 2011, vol. 353, # 6, p. 913 - 917
[13] Chemistry - A European Journal, 2011, vol. 17, # 27, p. 7409 - 7413
[14] Chemistry - A European Journal, 2012, vol. 18, # 31, p. 9645 - 9650
[15] Organic Letters, 2016, vol. 18, # 10, p. 2443 - 2446
[16] Tetrahedron, 2016, vol. 72, # 37, p. 5707 - 5712
[17] Patent: JP5793025, 2015, B2, . Location in patent: Paragraph 0037
[18] Organic Letters, 2017, vol. 19, # 13, p. 3478 - 3481
[19] Patent: CN107759634, 2018, A, . Location in patent: Paragraph 0036; 0037; 0043; 0044
[20] Synthesis (Germany), 2018, vol. 50, # 16, p. 3187 - 3196

2
[ 74-83-9 ]
[ 1099-45-2 ]
[ 30018-16-7 ]

Reference： [1] Journal of Organic Chemistry, 2014, vol. 79, # 22, p. 11161 - 11169

[ 30018-16-7 ] Synthesis Path-Downstream 1~88

1
[ 53163-53-4 ]
[ 30018-16-7 ]
[ 5056-14-4 ]

Reference： [1]Helvetica Chimica Acta,1957,vol. 40,p. 1242,1246

2
[ 85-44-9 ]
[ 30018-16-7 ]
[ 123120-12-7 ]
[ 123120-13-8 ]

Reference： [1]Synthetic Communications,1994,vol. 24,p. 1179 - 1186

3
[ 30018-16-7 ]
[ 21382-82-1 ]

Yield	Reaction Conditions	Operation in experiment
76.3%	With potassium hydroxide; In dichloromethane; water; at 20℃; for 0.333333h;	3g of compound 26 dissolved in 30mL of dichloromethane was added 26mL2N aqueous potassium hydroxide solution, the reaction mixture was stirred vigorously at room temperature 20min, the reaction was completed, the layers were separated and the organic layer was dried over anhydrous magnesium sulfate, filtration, spin dry organic solvent to give a white solid 1.87g, yield 76.3%.
	With water; sodium hydroxide;Cooling with ice;	A 500 mL flask was charged with PPh3 (26.2 g, 100 mmol) and 250 mL of toluene. To this solution was added ethyl 2-bromopropionate (100 mmol) over 40 minutes. The soultion was stirred for 8-9 hour at 75 C. The precipitate was filtered, washed with toluene (3×10 mL) and dried. The collected phosphonium salt was dissolved in H2O (400 mL) and 1drop of phenolphthalein solution was added. The mixture was cooled in an ice bath and saturated aqueous NaOH solution was added dropwise until a permanent pink color was obtained. The solid was filtered and washed with cold H2O, collected and dried in vacuo to afford 2d-1 (yield: 90%).
44.7 g	With sodium hydroxide; In hexane; water; at 0 - 40℃; for 4h;Inert atmosphere;	In a 1 L four-necked flask equipped with a stirrer and a thermometer and purged with nitrogen, an aqueous solution of (1-ethoxycarbonylethyl) triphenylphosphonium bromide[Prepared from 36.2 g (138 mmol) of triphenylphosphane, 400 ml of water and 25.0 g (138 mmol) of ethyl 2-bromopropanoate]And 50 ml of hexane, And 55.2 g (138 mmol) of a 10% sodium hydroxide aqueous solution was slowly added dropwise over 2 hours at a temperature condition of 30 to 40 C., followed by stirring at 30 to 40 C. for 1 hour, and further And the mixture was stirred at 0 to 10 C. for 1 hour. The precipitated crystals were separated by filtration, and the crystals were washed once with 50 ml of hexane and twice with 50 ml of water. 44.7 g (yield 89.3%, purity 98.0%) of ethyl 2- (triphenylphosphoranylidene) propanoate as a pale yellow crystal was obtained by drying the obtained crystal at a temperature of 60 C. or lower Obtained.

112 g	With sodium hydroxide; In water; at 20 - 50℃; for 6h;Inert atmosphere;	dd ethoxycarbonylethyltriphenylphosphonium bromide (144g) to water at 20-30C.Nitrogen filling,Heat to 40-50C,An aqueous solution of sodium hydroxide (27 g) was added,Insulation 6h;Reaction liquid cooling,Suction filtrationThe filter cake is washed with water,Dry to give carbamoylethylene triphenylphosphine (112 g).
	With sodium hydroxide; In chloroform; water; at 20℃;	General procedure: A dry two-necked flask was charged with a stirring bar, 3,5-dimethylphenol (1.22 g, 10 mmol), CH2Cl2 (30 mL), and pyridine (1.77 mL, 22 mmol). The mixture was cooled to 0 C, and bromoacetyl bromide (0.86 mL, 10 mmol) was added to the mixture slowly. The mixture was warmed to r.t. and stirred overnight. After the completion of the reaction (TLC monitoring), the mixture was washed with H2O (2 × 20 mL) and the organic phase was dried (Na2SO4). The solvent was removed and the residue was purified by flash chromatography on silicagel (c-Hex/EtOAc 10:1) to give 3,5-dimethylphenyl 2-bromoacetate (2.1 g, 86%) as a colorless oil. A dry two-neck flask was charged with PPh3 (786 mg, 3.0 mmol) and CHCl3 (10 mL). The solution was cooled to 0 C and the above prepared 3,5-dimethylphenyl 2-bromoacetate (729 mg, 3.0 mmol) was added. The reaction was warmed to r.t. and stirred overnight. The mixture was washed with aq 2 N NaOH (2 × 20 mL) and the collected organic phase was dried (Na2SO4). After removal of solvent under vacuum, the intermediate pure ylide was obtained as a white solid (1.20 g, 95%) and used in the next step without further purification. A dry Schlenk tube was charged with a stirring bar, CH2Cl2 (6 mL), the above prepared ylide (2.0 mmol), and Et3N (305 muL, 2.2 mmol). The mixture was cooled to 0 C in ice bath. A solution of acetyl chloride (2.2 mmol) in CH2Cl2 (2 mL) was added dropwise to the reaction mixture. The mixture was warmed to r.t. and stirred overnight. After the completion of the reaction (TLC monitoring), most of solvent was removed under vacuum, and Et2O (50 mL) was added to the flask, and the mixture was stirred for 0.5 h (Caution: longer reaction time may promote the isomerization of allenoate to the corresponding alkyl ester). The mixture was filtered and the organic phase was concentrated under vacuum. The residue was purified by flash chromatographyon silica gel (c-Hex/EtOAc 20:1) to give the allenoate 1e; yield: 147 mg (78%).
	With sodium hydroxide; for 0.5h;	A solution of compound 95 (135.42 g, 305.7 mmol) in dichloromethane (500 mL) was added slowly into 10%NaOH solution (450 mL) with vigorous stirring. The organic solution rapidly turned bright yellow. After 30 minutes, TLC analysis showed that the reaction was completed. Layers were separated and the aqueous layer was further extracted with CH 2Cl 2 (2 × 200 mL) . Combined organic layers were washed with brine, dried over anhydrous Na 2SO 4 and concentrated to give a yellow solid 96 (104 g, 94%yield) . MS ESI m/z calcd for C 23H 24O 2P [M+H] + 362.14, found 363.13. The crude product was used directly in the next step.

Reference： [1]Tetrahedron,2010,vol. 66,p. 4745 - 4759
[2]Journal of the American Chemical Society,2019,vol. 141,p. 1135 - 1140
[3]Chemistry - A European Journal,2015,vol. 21,p. 7408 - 7412
[4]Angewandte Chemie - International Edition,2018,vol. 57,p. 7240 - 7244
Angew. Chem.,2018,p. 7360 - 7364,5
[5]Patent: CN103864753,2016,B .Location in patent: Paragraph 0087; 0113-0114
[6]Chemical Communications,2019,vol. 55,p. 7009 - 7012
[7]Tetrahedron,1991,vol. 47,p. 2991 - 2998
[8]Organic Letters,2010,vol. 12,p. 240 - 243
[9]Tetrahedron,2016,vol. 72,p. 5707 - 5712
[10]Patent: JP5793025,2015,B2 .Location in patent: Paragraph 0029
[11]Patent: CN107759634,2018,A .Location in patent: Paragraph 0034; 0035; 0038; 0039; 0041; 0042; 0045; 0046
[12]Synthesis,2018,vol. 50,p. 3187 - 3196
[13]Patent: WO2019/127607,2019,A1 .Location in patent: Page/Page column 10; 164-165

4
[ 30018-16-7 ]
[ 79-03-8 ]
[ 24642-00-0 ]

Yield	Reaction Conditions	Operation in experiment
65%	With triethylamine; In dichloromethane; at 20℃;Inert atmosphere;	Procedure: (1-(ethoxycarbonyl) ethyl)triphenylphosphonium bromide (3.0 g, 6.80 mmol) was dissolved in 70.0 ml DCM in a flame dried flask under argon. It was cooled to 0C and triethylamine (2.00 ml, 14.30 mmol) was added. DCM solution of propionyl chloride (0.71 ml, 8.10 mmol) was added over an hour using addition funnel. The reaction mixture was allowed to stir for overnight at room temp during which time a precipitate forms, resulting in a cloudy heterogeneous mixture. After reaction is complete, excess hexane was added and stirred for additional 3 hours before DCM was evaporated. Hexane was added again and DCM was evaporated as much as possible. Crude reaction mixture was then transferred to a silica column for purification with (5-10% hexane/EtOAc) to have 65% yield.

Reference： [1]Helvetica Chimica Acta,1980,vol. 63,p. 438 - 455
[2]Tetrahedron Letters,2017,vol. 58,p. 106 - 108
[3]Chemical Communications,2011,vol. 47,p. 424 - 426

5
[ 30018-16-7 ]
[ 75-36-5 ]
[ 5717-41-9 ]

Reference： [1]Helvetica Chimica Acta,1980,vol. 63,p. 438 - 455
[2]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917
[3]Chemistry - A European Journal,2011,vol. 17,p. 7409 - 7413
[4]Chemistry - A European Journal,2012,vol. 18,p. 9645 - 9650
[5]Journal of Organic Chemistry,2014,vol. 79,p. 11161 - 11169
[6]Organic Letters,2016,vol. 18,p. 2443 - 2446

6
[ 30018-16-7 ]
[ 2528-61-2 ]
[ 5750-12-9 ]

Reference： [1]Helvetica Chimica Acta,1980,vol. 63,p. 438 - 455

7
[ 603-35-0 ]
[ 535-11-5 ]
[ 30018-16-7 ]

Yield	Reaction Conditions	Operation in experiment
80.5%	In ethyl acetate; at 20℃; for 24h;	The 1g of triphenylphosphine were dissolved in 15mL ethyl acetate was added 2-bromopropionate ethyl ester0.55mL2-, the reaction was stirred at room temperature 24h, and gradually a large amount of white solid was suction filtered, rinsed with ethyl acetate to give 1.35 g of a white solid, yield rate of 80.5%.
80%	at 50℃;Inert atmosphere;	In a 500 mL round-bottomed flask equipped with a magnetic stir bar was added triphenylphosphine (100 g, 381 mmol, 1.0 eq. ) and ethyl 2-bromopropionate (100 mL, 762 mmol, 2.0 eq. ) . The mixture was then heated to 50 under N 2 atmosphere overnight. After the white solid (PPh 3) was dissolved, a large amount of white solid was generated. Trituration with petroleum ether/EtOAc and filtration gave compound 95 as a white solid (135 g, 80%yield) . MS ESI m/z calcd for C 23H 24O 2P [M-Br] + 363.15, found 363.13.
	In toluene; at 75℃;	A 500 mL flask was charged with PPh3 (26.2 g, 100 mmol) and 250 mL of toluene. To this solution was added ethyl 2-bromopropionate (100 mmol) over 40 minutes. The soultion was stirred for 8-9 hour at 75 C. The precipitate was filtered, washed with toluene (3×10 mL) and dried. The collected phosphonium salt was dissolved in H2O (400 mL) and 1drop of phenolphthalein solution was added. The mixture was cooled in an ice bath and saturated aqueous NaOH solution was added dropwise until a permanent pink color was obtained. The solid was filtered and washed with cold H2O, collected and dried in vacuo to afford 2d-1 (yield: 90%).

	In water; at 75 - 80℃; for 4h;Inert atmosphere;	36.2 g (138 mmol) of triphenylphosphane and 400 ml of water were placed in a 500 ml four-necked flask equipped with a stirrer and a thermometer and purged with nitrogen, and 25.0 g (138 mmol) of ethyl 2-bromopropanoate was added to 75 To 80 C., and the mixture was stirred at 80 C. for 4 hours. The obtained aqueous solution was washed twice with 50 ml of toluene to obtain an aqueous solution of (1-ethoxycarbonylethyl) triphenylphosphonium bromide.
144 g	With potassium iodide; In water; toluene; at 20 - 75℃; for 15h;	At 20-30C,To a solution of triphenylphosphine (88 g) in toluene (the organic phase recovered in the first step of Example 3), an aqueous solution of potassium iodide (3 g) was added (the mother liquor from the first step of Example 3).Then alpha-bromo-propionic acid ethyl ester (60 g) is added,Reaction at 70-75 C for 15h;After the reaction is complete,Phase,Water cooling,Crystallization,Filtered to give the ethoxycarbonyl ethyl triphenylphosphonium bromide (144g);Organic phase recovery application,Aqueous mother liquor recovery application.
	In chloroform; at 0 - 20℃;	General procedure: A dry two-necked flask was charged with a stirring bar, 3,5-dimethylphenol (1.22 g, 10 mmol), CH2Cl2 (30 mL), and pyridine (1.77 mL, 22 mmol). The mixture was cooled to 0 C, and bromoacetyl bromide (0.86 mL, 10 mmol) was added to the mixture slowly. The mixture was warmed to r.t. and stirred overnight. After the completion of the reaction (TLC monitoring), the mixture was washed with H2O (2 × 20 mL) and the organic phase was dried (Na2SO4). The solvent was removed and the residue was purified by flash chromatography on silicagel (c-Hex/EtOAc 10:1) to give 3,5-dimethylphenyl 2-bromoacetate (2.1 g, 86%) as a colorless oil. A dry two-neck flask was charged with PPh3 (786 mg, 3.0 mmol) and CHCl3 (10 mL). The solution was cooled to 0 C and the above prepared 3,5-dimethylphenyl 2-bromoacetate (729 mg, 3.0 mmol) was added. The reaction was warmed to r.t. and stirred overnight. The mixture was washed with aq 2 N NaOH (2 × 20 mL) and the collected organic phase was dried (Na2SO4). After removal of solvent under vacuum, the intermediate pure ylide was obtained as a white solid (1.20 g, 95%) and used in the next step without further purification. A dry Schlenk tube was charged with a stirring bar, CH2Cl2 (6 mL), the above prepared ylide (2.0 mmol), and Et3N (305 muL, 2.2 mmol). The mixture was cooled to 0 C in ice bath. A solution of acetyl chloride (2.2 mmol) in CH2Cl2 (2 mL) was added dropwise to the reaction mixture. The mixture was warmed to r.t. and stirred overnight. After the completion of the reaction (TLC monitoring), most of solvent was removed under vacuum, and Et2O (50 mL) was added to the flask, and the mixture was stirred for 0.5 h (Caution: longer reaction time may promote the isomerization of allenoate to the corresponding alkyl ester). The mixture was filtered and the organic phase was concentrated under vacuum. The residue was purified by flash chromatographyon silica gel (c-Hex/EtOAc 20:1) to give the allenoate 1e; yield: 147 mg (78%).

Reference： [1]European Journal of Organic Chemistry,2016,vol. 2016,p. 2110 - 2114
[2]Chemistry - A European Journal,2015,vol. 21,p. 7408 - 7412
[3]Tetrahedron,2010,vol. 66,p. 4745 - 4759
[4]Journal of Organic Chemistry,1984,vol. 49,p. 4293 - 4295
[5]Organic and Biomolecular Chemistry,2019,vol. 17,p. 6374 - 6385
[6]Patent: CN103864753,2016,B .Location in patent: Paragraph 0087; 0110-0111
[7]Patent: WO2019/127607,2019,A1 .Location in patent: Page/Page column 10; 164
[8]Angewandte Chemie - International Edition,2018,vol. 57,p. 7240 - 7244
Angew. Chem.,2018,p. 7360 - 7364,5
[9]Journal of the American Chemical Society,2019,vol. 141,p. 1135 - 1140
[10]Tetrahedron,1991,vol. 47,p. 2991 - 2998
[11]Journal of Fluorine Chemistry,1985,vol. 29,p. 363 - 384
[12]Organic and Biomolecular Chemistry,2004,vol. 2,p. 1456 - 1470
[13]Organic Letters,2010,vol. 12,p. 240 - 243
[14]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917
[15]Chemistry - A European Journal,2011,vol. 17,p. 7409 - 7413
[16]Organic Letters,2016,vol. 18,p. 2443 - 2446
[17]Tetrahedron,2016,vol. 72,p. 5707 - 5712
[18]Patent: JP5793025,2015,B2 .Location in patent: Paragraph 0037
[19]Organic Letters,2017,vol. 19,p. 3478 - 3481
[20]Patent: CN107759634,2018,A .Location in patent: Paragraph 0036; 0037; 0043; 0044
[21]Synthesis,2018,vol. 50,p. 3187 - 3196
[22]Chemical Communications,2019,vol. 55,p. 7009 - 7012

8
[ 30018-16-7 ]
[ 103-80-0 ]
[ 5750-22-1 ]

Reference： [1]Helvetica Chimica Acta,1980,vol. 63,p. 438 - 455
[2]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

9
[ 51934-41-9 ]
[ 30018-16-7 ]
3-formyl-4-methoxyphenylboronic acid [ No CAS ]
(E)-ethyl 3-(5'-[4"-ethoxycarbonylphenyl]phenyl)methacrylate [ No CAS ]

Reference： [1]New Journal of Chemistry,2006,vol. 30,p. 359 - 369

10
[ 444622-08-6 ]
[ 30018-16-7 ]
3-{2-isopropyl-3-[4-(2,2,2-trifluoro-1-hydroxy-1-trifluoromethyl-ethyl)-phenyl]-3<i>H</i>-imidazol-4-yl}-2-methyl-acrylic acid ethyl ester [ No CAS ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 695 - 700

11
[ 30018-16-7 ]
[ 203912-53-2 ]

Reference： [1]Archiv der Pharmazie,2001,vol. 334,p. 53 - 61

12
[ 30018-16-7 ]
[ 134411-37-3 ]

Reference： [1]Journal of Organic Chemistry,1998,vol. 63,p. 2948 - 2953
[2]Tetrahedron,1991,vol. 47,p. 2991 - 2998

13
[ 30018-16-7 ]
3'-ethyl-3,2'-dimethyl-[2,2']bioxiranyl-3-carboxylic acid ethyl ester [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1998,vol. 63,p. 2948 - 2953

14
[ 30018-16-7 ]
(R,R)-2-[(E)-2-(ethoxycarbonyl)-2-methylvinyl]-3-ethyl-2-methyloxirane [ No CAS ]

Reference： [1]Journal of Organic Chemistry,1998,vol. 63,p. 2948 - 2953

15
[ 30018-16-7 ]
[ 134411-38-4 ]

Reference： [1]Tetrahedron,1991,vol. 47,p. 2991 - 2998

16
[ 849239-19-6 ]
[ 30018-16-7 ]
[ 849239-28-7 ]

Yield	Reaction Conditions	Operation in experiment
86%	With n-butyllithium; In tetrahydrofuran; hexane; at 0 - 20℃; for 2h;	Ethyl (2E)-3-{5-[4-(benzyloxy)phenyl]-1-cyclohexyl-1H-pyrazol-3-yl}-2-methyl-2-propenoate (4.1). BuLi (1.6 M in hexanes, 956 muL, 1.53 mmol) was added dropwise to (1-ethoxycarbonyl-thyl)triphenylphosphonium bromide (738 mg, 1.66 mmol) in THF (7 ml) at 0 C., follow by addition of aldehyde 2.2 (500 mg, 1.39 mmol as solution in 3 ml of THF). The mixture was stirred at 0 C. for 30 min and warmed to rt, and after 1.5 h, H2O was added. The mixture was diluted with EtOAc, and the organic phase was washed with H2O, brine, dried (Na2SO4). After being concentrated, the resultant residue was purified by SiO2 chromatography (gradient elution: 10 to 15% EtOAc/hexanes) to provide 530 mg (86%) of 4.1. MS (ESI) 445.4 (MH+).

Reference： [1]Patent: US2005/75376,2005,A1 .Location in patent: Page/Page column 24-25
[2]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 2869 - 2872

17
[ 5056-17-7 ]
[ 30018-16-7 ]
[ 908001-05-8 ]

Yield	Reaction Conditions	Operation in experiment
> 70%	In butylene oxide; toluene; at 100℃; for 24h;	First Coupling Reaction to Form Compound M; Compound A was treated with 1 eq. C-3 phosphonium bromide (Compound K) at 100 C. for 1 day. This coupling reaction was performed in butylene oxide/toluene 2:1 (0.7 ml+1.4 ml/mmol) and showed good product formation. While cooling to room temperature and later to 0 C., no precipitation was observed. The orange mixture was then filtered over silica gel (0.33 g/mmol). The filter cake was washed with toluene (1.7 ml/mmol). The filtrates were combined and evaporated to dryness at JT=45 C. to give a crude product that appeared as an orange oil. Next, the reaction mixture was evaporated to dryness. The residue was slurried in MeOH to obtain the crude product in solid form and then washed with MeOH (3×). The quality of the crude product obtained was poor due to the presence of C16 diethylester in addition to the desired C13 mono coupling product, Compound M. Thus, a purification step over silica gel with 10:1 methylcyclohexane/EtOAc was performed. The crude product was dissolved in dicloromethane (0.3 ml/g crude product). The C-16 diethyl ester (about 7%) was the first compound to elute. Once this step was performed, the yield was 45% (20 g experiment). On a smaller-scale, yields were as high as 70%. The best quality product was determined to have 98.1% a/a trans isomer at a detection wavelength of 383 nm (9.22 min). An additional compound was present (1.7% a/a, 9.47 min) which was suspected to be a cis isomer of Compound M.

Reference： [1]Patent: US2006/194973,2006,A1 .Location in patent: Page/Page column 25

18
[ 5056-17-7 ]
[ 30018-16-7 ]
[ 908001-08-1 ]

Yield	Reaction Conditions	Operation in experiment
61 - 62%	In butylene oxide; toluene; at 100℃; for 22h;Product distribution / selectivity;	Coupling Reaction to Form Compound Q (Using Compound K as a Reactant); In a second experiment to synthesize Compound Q, Compound K was substituted for compound L in the coupling reaction. This substitution showed a better overall reaction conversion. The coupling reaction between Compound A and Compound K was performed in a mixture of butylene oxide/toluene 2:1 (0.9 ml+1.8 ml/mmol) and showed good product formation with 3 eq. Wittig reagent at JT=100 C. (22 h). The yellow product was isolated by filtration at 0 C. and by washing twice with methylcyclohexane. The yield was 61-62% (10 g scale). HPLC analysis showed a purity of Compound Q at 85.2% ala trans isomer at 369 nm (13.3 min) with the major impurity being a cis isomer.

Reference： [1]Patent: US2006/194973,2006,A1 .Location in patent: Page/Page column 26-27

19
[ 908001-10-5 ]
[ 30018-16-7 ]
[ 908001-13-8 ]

Yield	Reaction Conditions	Operation in experiment
56%	In butylene oxide; toluene; at 100℃;	Second Coupling Reaction to Form Compound V; The second coupling reaction was performed by reacting Compound S (also known as the C15 monoester) with 1.5 eq. Compound K (a C-3 phoshonium bromide) at 100 C. This coupling reaction was performed in butylene oxide/toluene 2:1 (0.6 ml+1.2 ml/mmol) and showed a good product formation. An orange product was isolated by filtration at 0 C. and by two washing steps in methylcyclohexane. The yield for this step was 56% (9 g scale). The quality of Compound V was measured using HPLC and found to be 96.7% a/a trans isomer at a detection wavelength of 369 nm (14.2 min). In addition, the major impurity observed (1.7% a/a, 13.6 min) is speculated to be a cis-isomer of Compound V.

Reference： [1]Patent: US2006/194973,2006,A1 .Location in patent: Page/Page column 29

20
[ 110-63-4 ]
[ 30018-16-7 ]
(2E,6E)-2,7-Dimethyl-octa-2,6-dienedioic acid diethyl ester [ No CAS ]
[ 70562-20-8 ]
[ 70562-19-5 ]

Reference： [1]Synlett,2008,p. 649 - 652

21
[ 71778-56-8 ]
[ 30018-16-7 ]
(2Z,6E)-2-Methyl-octa-2,6-dienedioic acid diethyl ester [ No CAS ]
[ 123718-07-0 ]

Reference： [1]Synlett,2008,p. 649 - 652

22
[ 67081-18-9 ]
[ 30018-16-7 ]
C₁₄H₂₂O₄ [ No CAS ]
C₁₄H₂₂O₄ [ No CAS ]

Reference： [1]Synlett,2008,p. 649 - 652

23
[ 30018-16-7 ]
[ 504-63-2 ]
(Z)-5-hydroxy-2-methyl-pent-2-enoic acid ethyl ester [ No CAS ]
(E)-5-hydroxy-2-methyl-pent-2-enoic acid ethyl ester [ No CAS ]
[ 876478-45-4 ]

Reference： [1]Synlett,2008,p. 649 - 652

24
[ 58550-34-8 ]
[ 30018-16-7 ]
[ 22388-91-6 ]

Yield	Reaction Conditions	Operation in experiment
73%		To a cooled suspension of (1-ethoxycarbonylethyl) triphenylphosphonium bromide (1.0 g, 2.25 mmol) in dry THF (10 mL) was added dropwise n-butyllithium (1.6 M in hexanes, 1.4 mL, 2.3 mmol) at 0 C. Stirring was continued at 0 C for 20 min, then 10 min at 20 C. To the above solution was added (E)-2-METHYL-3- (4-NITROPHENYL) propenal (4b) (0.36 g, 1.88 mmol) in portions over 5 min. The mixture was then stirred at 20 C for 16 h. The mixture was then evaporated and the residue purified by flash chromatography on silica gel (1 : 4 ethyl acetate: 60-80 C petroleum ether) to give a residue that was recrystallised from methanol to give the title compound (0.38 g, 73%) as yellow platelets, mp 80-81 C ; IR (nujol) VU"1697 (COOEt), 1606 and 1589 (C=C), 1508 (NO2) CM ;1H NMR (300 MHz, CDCL3) UH8. 16 (2H, d, J=9.0 Hz, ArH), 7.37 (2H, d, J=9.0 Hz, ARH), 7.19 (1H, s, CH=CH-COO), 6.54 (1H, s, Ph-CH), 4.14 (2H, q, J=7 Hz, CH2O), 2.03 (6H, s, =CCH3), 1.29 (3H, t, J=7 Hz, CH3CH2O) ; 13C NMR (75 MHz, CDCl3) 5C 168.91 (COO), 144.13, 142.29, 138,48, 131.75, 130.16, 129.18, 123.97 (ARC=C and C=C), 61.34 (CH2O), 18.97, 14.74, 14.68 (CH3). Elemental analysis: CL5HL7NO4. CALC. (%) C: 65.45, H: 6.18, N: 5.09. Found (%) C: 64.93, H: 6.15, 4.88.

Reference： [1]Patent: WO2005/11661,2005,A1 .Location in patent: Page 36; 37

25
[ 37859-24-8 ]
[ 30018-16-7 ]
[ 189626-02-6 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

26
[ 1871-76-7 ]
[ 30018-16-7 ]
[ 5717-43-1 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

27
[ 764-85-2 ]
[ 30018-16-7 ]
[ 869885-19-8 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

28
[ 25145-43-1 ]
[ 30018-16-7 ]
[ 5717-44-2 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

29
[ 36854-57-6 ]
[ 30018-16-7 ]
[ 38701-07-4 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

30
[ 30018-16-7 ]
[ 35675-44-6 ]
[ 189626-00-4 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

31
[ 30018-16-7 ]
[ 25026-34-0 ]
ethyl 4-(p-chlorophenyl)-2-methyl-2,3-butadienoate [ No CAS ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

32
[ 30018-16-7 ]
[ 2719-27-9 ]
[ 5717-29-3 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

33
[ 30018-16-7 ]
[ 459-04-1 ]
[ 189626-04-8 ]

Reference： [1]Organic and Biomolecular Chemistry,2010,vol. 8,p. 274 - 281

34
[ 53448-07-0 ]
[ 30018-16-7 ]
ethyl (2E,4Z)-2-methyl-2,4-tridecadienoate [ No CAS ]
[ 1238375-02-4 ]

Reference： [1]Tetrahedron,2010,vol. 66,p. 4745 - 4759

35
[ 30018-16-7 ]
[ 89932-40-1 ]
[ 1203794-04-0 ]

Reference： [1]Journal of Combinatorial Chemistry,2010,vol. 12,p. 141 - 150

36
[ 30018-16-7 ]
[ 1269206-44-1 ]
(3,4-trans)-ethyl 1-benzyl-3-methyl-4-vinylpyrrolidine-3-carboxylate [ No CAS ]
C₂₆H₃₄N₂O₂ [ No CAS ]

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 872 - 874

37
[ 30018-16-7 ]
[ 107-02-8 ]
[ 75088-96-9 ]

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 872 - 874

38
[ 72155-45-4 ]
[ 30018-16-7 ]
[ 244033-72-5 ]

Reference： [1]European Journal of Organic Chemistry,2009,p. 6367 - 6378

39
[ 30018-16-7 ]
[ 1262884-16-1 ]
C₁₄H₂₅BO₄ [ No CAS ]

Reference： [1]Chemical Communications,2011,vol. 47,p. 424 - 426

40
[ 84371-41-5 ]
[ 30018-16-7 ]
C₃₉H₆₄O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		A suspension of (1-(ethoxycarbonyl)ethyl) triphenylphosphonium bromide14 (21.40 g, 48.27 mmol) in dry THF (100 mL) was reacted with potassium t-butoxide (44.0 ml, 1 M in THF) at room temperature overnight. A solution of the aldehyde 7 (8.00 g, 14.68 mmol) in dry THF (100 mL) was then added and refluxed for 4 h. The reaction mixture was allowed to cool at room temperature, was diluted with hexane (100 mL) and H2O/MeOH (150 mL, 1:1, v/v), and the resulting solution was extracted with EtOAc (2×100 mL). The combined organic layers were washed with brine (100 mL), dried over Na2SO4 and evaporated under reduced pressure. The residual brown oil was dissolved in 5% HCl in MeOH (150 mL) and stirred at room temperature for 2 h. The solvent was removed under reduced pressure, the residue was dissolved in H2O (120 mL) and extracted with CHCl3 (3×60 mL). The combined organic layers were washed with H2O (80 mL), brine (80 mL), dried over Na2SO4 and evaporated under reduced pressure. The crude was purified by flash chromatography to obtain ethyl 3alpha,6alpha-dihydroxy-25-methyl-24-bishomo-5beta-chol-24-en-26-oate as white solid. The ester thus obtained was dissolved in 60 mL of 5% NaOH in MeOH and the resulting mixture was stirred at 60 C overnight. The solvent was evaporated under reduced pressure, the residue was dissolved into H2O (100 mL), acidified with 3N HCl and extracted with EtOAc (3×60 mL). The combined organic layers were washed with H2O (100 mL), brine (100 mL), dried over Na2SO4 and evaporated under reduced pressure to afford the desired acid 8 (5.70 g, 13.17 mmol, 89%, E/Z>20/1) as pure white solid.

Reference： [1]Tetrahedron,2011,vol. 67,p. 1924 - 1929

41
[ 30018-16-7 ]
[ 1308874-49-8 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

42
[ 30018-16-7 ]
[ 1308874-50-1 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

43
[ 30018-16-7 ]
[ 1308874-51-2 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

44
[ 30018-16-7 ]
[ 1308874-56-7 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

45
[ 30018-16-7 ]
[ 1308874-58-9 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

46
[ 30018-16-7 ]
[ 1308874-61-4 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

47
[ 30018-16-7 ]
[ 1308874-63-6 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

48
[ 30018-16-7 ]
[ 1308874-64-7 ]

Reference： [1]Advanced Synthesis and Catalysis,2011,vol. 353,p. 913 - 917

49
[ 1308870-06-5 ]
[ 30018-16-7 ]
[ 1309365-69-2 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In ethanol; at 80℃; for 1h;	Step 4:; A 500 mL RBF was charged with (l-ethoxy-l -oxopropan-2- yl)triphenylphosphonium bromide (13.75 g, 31.0 mmol) 6-bromo-2-(teri- butylamino)quinoline-3-carbaldehyde (8.58 g, 27.9 mmol, prepared as in Example 15, Step 3), potassium carbonate (6.43 g, 46.5 mmol), and 100 mL of EtOH. The mixture was heated to 80 C for 1 h then cooled to RT and concentrated. The resulting oil was purified via silica gel column chromatography (0-15% EtOAc in hexanes) to give (E)- ethyl 3-(6-bromo-2-(?er?-butylamino)quinolin-3-yl)-2-methylacrylate as a yellow solid.

Reference： [1]Patent: WO2011/63233,2011,A1 .Location in patent: Page/Page column 75

50
[ 849239-60-7 ]
[ 30018-16-7 ]
[ 1310458-93-5 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2011,vol. 21,p. 2869 - 2872

51
[ 30018-16-7 ]
C₃₁H₂₉ClN₂O₄ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2011,vol. 17,p. 7409 - 7413

52
[ 30018-16-7 ]
C₃₁H₂₉BrN₂O₄ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2011,vol. 17,p. 7409 - 7413

53
[ 51987-73-6 ]
[ 30018-16-7 ]
[ 244033-72-5 ]

Yield	Reaction Conditions	Operation in experiment
83%		L-t-l3oc-phenylalanine methyl ester 326 (5.60 g,20.05 mmol) in CH2C12 (80 ml) at -78 C. was added dropwise DIHAL (40 ml, 40 mmol, 1.0 M) in CH2C12. After stirred at -78 C. for 45 mm, the ylide solution prepared from 1 -(1 -ethoxycarbonyl ethyl)-triphenylphosphonium bromide (18.0 g, 40.64 mmol) and KOtHu (5.00 g, 44.64 mmol) in CH2C12 (80 ml) at RT was added at -78 C. After stirred at -78 C. for 1 h and RT over night, the mixture was poured into 1 L of NaH2PO4 (sat.) solution with vigorously stirring. Separated and the aqueous phase was extracted with CH2C12. The organic layers were dried over Na2504, concentrated and purified by 5i02 chromatography (EtOAc/ Hexane, 1:7.-1:5) to afford 5.50 g (83% yields) of the title compound. ESI: mlz: [M+Na], calcd for C19H27NNaO4, 356.19, Found, 356.20.
83%		Example 64. (S, E)-Ethyl 5-phenyl-4-(tert-butoxy-carbonylamino)-2-methylpent-2-enoate (327) L-t-Boc-phenylalanine methyl ester 326 (5.60 g, 20.05 mmol) in CH2Cl2 (80 ml) at -78 C. was added dropwise DIBAL (40 ml, 40 mmol, 1.0 M) in CH2Cl2. After stirred at -78 C. for 45 min, the ylide solution prepared from <strong>[30018-16-7]1-(1-ethoxycarbonyl ethyl)-triphenylphosphonium bromide</strong> (18.0 g, 40.64 mmol) and KOtBu (5.00 g, 44.64 mmol) in CH2Cl2 (80 ml) at RT was added at -78 C. After stirred at -78 C. for 1 h and RT over night, the mixture was poured into 1 L of NaH2PO4 (sat.) solution with vigorously stirring. Separated and the aqueous phase was extracted with CH2Cl2. The organic layers were dried over Na2SO4, concentrated and purified by SiO2 chromatography (EtOAc/Hexane, 1:7?1:5) to afford 5.50 g (83% yields) of the title compound. ESI: m/z: [M+Na]+, calcd for C19H27NNaO4, 356.19, Found, 356.20.
82%		1.6. (4S,2E)-4-(tert.-Butoxycarbonylamino)-2-methyl-5-phenyl-2-pentenic acid ethyl ester (8): To a solution of 4.90 g of L-Boc-phenylalanine methyl ester (17.5 mmol, 1.0 eq.) in 50 ml of absolute dichloromethane, 35 ml of a 1 M DIBAlH solution (35 mmol, 2.0 eq.) is added slowly dropwise at -78 C. While the reaction mixture is stirred at -78 C. for 30 min, the ylide solution is prepared from 15.5 g of (1-ethoxycarbonyl-ethyl)-triphenylphosphonium bromide (35.0 mmol, 2.0 eq.) and 4.03 g of KOtBu (35.9 mmol, 2.1 eq.) in 40 ml of absolute dichloromethane at room temperature. The ylide is added dropwise to the aldehyde solution at -78 C., and after one hour, the cooling bath is removed, and stirring is performed over night at room temperature.The reaction mixture is poured into 800 ml of saturated potassium-sodium tartrate solution and stirred vigorously for 30 min. The aqueous phase is extracted with ethyl acetate, and the combined organic phases are dried over Na2SO4. Purification by column chromatography (hexane:EE 95:5, then 9:1) yields 4.78 g of the Wittig product (8) (14.3 mmol, 82% of theory) as a colorless oil, which congeals over night to give a white solid.Rf(8)=0.31 (hexane:EE 8:2) 1H NMR (500 MHz, CDCl3): delta=1.26 (t, 3J15,14=7.3 Hz, 3H, 15-H), 1.38 (s, 9H, 13-H), 1.68 (d, 4J10,3=1.5 Hz, 3H, 10-H), 2.76 (dd, 2J5a,5b=13.3 Hz, 3J5a, 4=7.0 Hz, 1H, 5-Ha), 2.90 (m, 1H, 5-Hb), 4.16 (q, 3J14,15=7.3 Hz, 2H, 14-H), 4.55 (bs, 1H, NH), 4.64 (bs, 1H, 4-H), 6.49 (dd, 3J3,4=9.1 Hz, 4J3,10=1.5 Hz, 1H, 3-H), 7.15 (d, 3J7,8=7.0 Hz, 2H, 7-H), 7.20 (t, 3J9,8=7.3 Hz, 1H, 9-H), 7.26 (dd, 3J8,7?3J8,9=7.2 Hz, 2H, 8-H).13C NMR (100 MHz, CDCl3): delta=12.5 (q, C-10), 14.2 (q, C-15), 28.3 (q, C-13), 41.1 (t, C-5), 50.1 (d, C-4), 60.6 (t, C-14), 79.6 (s, C-12), 126.6 (d, C-9), 128.4 (d, C-8), 129.2 (s, C-2), 129.5 (d, C-7), 136.7 (s, C-6), 140.2 (d, C-3), 154.9 (s, C-11), 167.7 (s, C-1).Melting point: 68 C.

Reference： [1]Patent: US2017/157262,2017,A1 .Location in patent: Paragraph 0326; 0327
[2]Patent: US2017/296663,2017,A1 .Location in patent: Paragraph 0319; 0320
[3]Patent: US2011/245295,2011,A1 .Location in patent: Page/Page column 10

54
[ 127793-62-8 ]
[ 30018-16-7 ]
(Z)-6-(tert-butyldiphenylsilanyloxy)-2-methylhex-2-enoic acid ethyl ester [ No CAS ]
[ 202581-32-6 ]

Reference： [1]Angewandte Chemie - International Edition,2012,vol. 51,p. 2111 - 2114

55
[ 30018-16-7 ]
C₃₄H₃₀N₄O₃ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2012,vol. 18,p. 9645 - 9650

56
[ 30018-16-7 ]
C₃₄H₂₉FN₄O₃ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2012,vol. 18,p. 9645 - 9650

57
[ 30018-16-7 ]
C₂₈H₂₅ClN₄O₃ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2012,vol. 18,p. 9645 - 9650

58
[ 30018-16-7 ]
C₃₂H₂₅ClN₄O₃ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2012,vol. 18,p. 9645 - 9650

59
[ 30018-16-7 ]
C₃₂H₂₅N₅O₅ [ No CAS ]

Reference： [1]Chemistry - A European Journal,2012,vol. 18,p. 9645 - 9650

60
C₁₄H₁₈INO₃ [ No CAS ]
[ 30018-16-7 ]
C₁₉H₂₆INO₄ [ No CAS ]

Reference： [1]Molecular BioSystems,2012,vol. 8,p. 2067 - 2075

61
3α,6α-bis(tetrahydropyranyloxy)-24-nor-5β-cholan-23-al [ No CAS ]
[ 30018-16-7 ]
C₃₈H₆₂O₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a suspension of <strong>[30018-16-7](1-(ethoxycarbonyl)ethyl)triphenylphosphonium bromide</strong> (9.65 g, 21.8 mmol) (prepared by refluxing ethyl 2-bromopropionate and PPh3 in benzene [43]) in dry THF (50 mL) potassium t-butoxide (19.8 mL, 1 M in THF) was added and the resulting mixture was stirred at room temperature over night. A solution of the aldehyde 17 (3.5 g, 6.6 mmol) in dry THF (40 mL) was then added and the resulting mixture was refluxed for 1 h. The reaction mixture was allowed to cool at room temperature, poured into H2O (100 mL)and extracted with EtOAc (2 × 70 mL). The combined organic layers were washed with brine (100 mL), dried over Na2SO4 and evaporated under reduced pressure. The resulting brown oil was dissolved in 5% HCl in MeOH (100 mL) and stirred at room temperature for 1 h. The solvent was then removed under reduced pressure, the residue was dissolved in H2O (120 mL) and extracted with CHCl3 (3 × 60 mL). The combined organic layers were washed with H2O (60 mL), brine (60 mL), dried over Na2SO4 and evaporated under reduced pressure. The crude was purified by flash chromatography eluting with petroleum ether/EtOAc from 0 to 20%. The resulting white solid was dissolved in 30 mL of 5% NaOH in MeOH and the resulting mixture was stirred at 60 C over night. The solvent was evaporated under reduced pressure, the residue was dissolved into H2O (100 mL), acidified with 3N HCl and extracted with EtOAc (3 × 60 mL). The combined organic layers were washed with H2O (100 mL), brine (100 mL), dried over Na2SO4 and evaporated under reduced pressure to afford the desired acid 18 (1.93 g, 4.62 mmol, 70%) as pure white solid.

Reference： [1]Molecules,2013,vol. 18,p. 10497 - 10513

62
[ 443761-67-9 ]
[ 30018-16-7 ]
C₁₂H₂₀O₃ [ No CAS ]

Reference： [1]Organic Process Research and Development,2004,vol. 8,p. 597 - 602

63
(1S,2R)-2-(1-tosyl-1H-indol-2-yl)cyclopropanecarbaldehyde [ No CAS ]
[ 30018-16-7 ]
(R)-ethyl 10-methyl-5-tosyl-5,6,7,10-tetrahydrocyclohepta[b]indole-10-carboxylate [ No CAS ]
(S)-ethyl 10-methyl-5-tosyl-5,6,7,10-tetrahydrocyclohepta[b]indole-10-carboxylate [ No CAS ]

Reference： [1]Organic Letters,2013,vol. 15,p. 5472 - 5475

64
(1R,2S)-2-(1-tosyl-1H-indol-3-yl)cyclopropane carbaldehyde [ No CAS ]
[ 30018-16-7 ]
(5aS,6R)-ethyl 6-methyl-5-tosyl-5,5a,6,9-tetrahydrocyclohepta[b]indole-6-carboxylate [ No CAS ]

Reference： [1]Organic Letters,2013,vol. 15,p. 5472 - 5475

65
[ 30018-16-7 ]
[ 123-38-6 ]
[ 16958-19-3 ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2014,vol. 53,p. 717 - 722

66
[ 30018-16-7 ]
1-tert-butyl 3-ethyl 2-(3-butylquinolin-2-yl)-2-methylmalonate [ No CAS ]