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Structure of 4206-67-1 * Storage: {[proInfo.prStorage]}
* 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.
Reference:
[1] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1989, p. 115 - 124
[2] Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1972-1999), 1980, p. 1493 - 1498
[3] Synthesis, 1980, # 4, p. 318 - 320
[4] Journal of Physical Organic Chemistry, 1999, vol. 12, # 7, p. 564 - 576
[5] Journal of the American Chemical Society, 1989, vol. 111, # 18, p. 7199 - 7205
[6] Journal of the American Chemical Society, 1946, vol. 68, p. 481,483
[7] Collection of Czechoslovak Chemical Communications, 1978, vol. 43, p. 3192 - 3201
[8] Journal of Organometallic Chemistry, 1976, vol. 111, p. 153 - 160
[9] Journal of the Chemical Society [Section] A: Inorganic, Physical, Theoretical, 1970, p. 2285 - 2291
[10] Journal of Organic Chemistry, 1997, vol. 62, # 24, p. 8595 - 8596
[11] Bulletin of the Chemical Society of Japan, 1999, vol. 72, # 4, p. 741 - 750
[12] Organic Letters, 2004, vol. 6, # 16, p. 2709 - 2711
[13] Journal of Materials Chemistry, 2010, vol. 20, # 38, p. 8224 - 8226
[14] Chemical Science, 2014, vol. 5, # 10, p. 3983 - 3994
[15] Organometallics, 2017, vol. 36, # 20, p. 3981 - 3986
3
[ 7681-82-5 ]
[ 2344-80-1 ]
[ 4206-67-1 ]
Reference:
[1] Journal of the American Chemical Society, [2] Journal of the American Chemical Society, 1946, vol. 68, p. 481 - 484
[3] , Gmelin Handbook: Si: MVol.C, 4, page 14 - 18,
[4] Journal of the American Chemical Society, 1947, vol. 69, p. 1976
[5] , Gmelin Handbook: Si: MVol.C, 3, page 11 - 14,
4
[ 186581-53-3 ]
[ 16029-98-4 ]
[ 4206-67-1 ]
Reference:
[1] Synthesis, 1988, # 4, p. 318 - 319
5
[ 75-77-4 ]
[ 75-47-8 ]
[ 4206-67-1 ]
[ 29955-07-5 ]
[ 29954-87-8 ]
Reference:
[1] Bulletin of the Chemical Society of Japan, 2004, vol. 77, # 8, p. 1581 - 1586
Reference:
[1] Doklady Akademii Nauk SSSR, 1954, vol. 94, p. 485[2] Chem.Abstr., 1955, p. 3795
14
[ 4206-67-1 ]
[ 100-46-9 ]
[ 53215-95-5 ]
Yield
Reaction Conditions
Operation in experiment
89%
With potassium carbonate In acetonitrile at 20℃; for 12 h;
General procedure: Individual solutions of benzylamine derivatives (24.3 mmol of 37 (2.6 g), 28.0 mmol of 38 (3.4 g), 28.0 mmol of 39 (3.8 g), 11.2 mmol of 40 (1.4 g), 11.2 mmol of 41(2.0 g)) in acetonitrile (120 mL) containing K2CO3 (5.2 g (37.4 mmol) for 37, 6.5 g ( 46.7 mmol) for38-39, and 2.6 g (18.7 mmol) for 40-41) and Me3SiCH2I (4.0 g (18.7 mmol) for 37, 5.0 g (23.4 mmol) for 38-39, and 2.0 g (9.3 mmol) for 40-41) were stirred for 12 h at room temperature and concentrated in vacuo to give residues which were triturated with CH2Cl2. The triturates were dried and concentrated in vacuo to afford residues, which were subjected to silica gel column chromatography (EtOAc: hexane = 1: 8 ~ 1: 15) to yield 421 (3.2 g, 89percent), 43 (3.85 g, 79percent), 442 (3.3g, 63percent), 45 (1.51 g, 76 percent), and 46 (1.9 g, 78 percent).
Reference:
[1] Tetrahedron Letters, 2015, vol. 56, # 23, p. 3014 - 3018
[2] Organic and Biomolecular Chemistry, 2016, vol. 14, # 44, p. 10502 - 10510
[3] Tetrahedron Letters, 2017, vol. 58, # 10, p. 949 - 954
[4] Tetrahedron, 2017, vol. 73, # 44, p. 6249 - 6261
To a suspension of LiAlH4 (36 mg, 0.96 mmol) in THF (mL) was added Z-Ile-N(OMe)Me (380 mg, 0.96 mmol) in THF (5 mL) at 0 C, stirred for 15 min at same temperature. The reaction was quenched with saturated aqueous H2O, filtered, and concentrated. The residue was roughly purified by silica gel column chromatography (hexane/AcOEt = 4:1) to give Z-Leu-al 19, which was immediately used for the next step without further purification. To a solution of methyltriphenylphosphonium bromide (686 mg, 1.92 mmol) in THF (5 mL) was added n-BuLi (1.3 mL, 2.1 mmol, 1.6 mol/L in hexane) at 0 C. The mixture was stirred for 1 h at room temperature, and then methyltrimethylsilyl iodide (286 muL, 1.92 mmol) was added at 0 C. The resultant mixture was stirred for 1 h at room temperature. n-BuLi (1.3 mL, 2.1 mmol, 1.6 mol/L in hexane) was added to the mixture at -78 C. The reaction mixture was stirred for 1 h at room temperature, and then Z-Leu-al 19 in ether (3 mL) was added. The resultant mixture was stirred for 1 h at room temperature. The reaction was quenched with saturated aqueous NH4Cl, and the whole was extracted with ether. The organic layer was washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was dissolved in THF (3 mL) and TBAF (0.96 mL, 0.96 mmol, 1.0 mol/L in THF) was added at 0 C and stirred for 1 h at room temperature. The reaction was quenched with saturated aqueous NH4Cl, and the whole was extracted with ether. The organic layer was washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was roughly purified by silica gel column chromatography (hexane/EtOAc = 3:1). The resultant residue was dissolved in acetone (8 mL) and 2,2-dimethoxypropane (2.5 mL) and BF3·Et2O (25 muL, 0.20 mmol) was added. The mixture was stirred for 5 h at room temperature. The reaction was quenched with Et3N at 0 C, filtered, and concentrated. The residue was purified by silica gel column chromatography (hexane/EtOAc = 6:1) to give 20 as a single diastereomer (663 mg, 18%, 3 steps).
General procedure: n-Butyllithium (6.5 ml of a 2.5 M solution in hexane, 16.0 mmol) is added dropwise with stirring over 0.5 h to a suspension of methyltriphenylphosphonium bromide (14.5 mmol) in dry tetrahydrofuran (25 ml) at 0 C under argon. The mixture is warmed to room temperature and stirred for 1 h, recooled to 0 C and iodomethyltrimethylsilane (14.5 mmol) is added over 10 min. The mixture is again allowed to come slowly to room temperature to precipitate the new phosphonium salt. After 1 h the reaction mixture is treated with a second equivalent of n-butyllithium (6.5 ml of a 2.5 M solution in hexane, 16.0 mmol) at -78 C. The mixture is allowed to warm slowly to room temperature and stirred for a further 1.5 h to give the dark red solution of the ylid, beta-trimethylsilylethylidenephosphorane. The (5alpha)-cholestan-3beta-one (12.9 mmol) in dry tetrahydrofuran (10 ml) is then added dropwise over 15 min to the ylid solution at -78 C under argon. After 0.5 h the mixture is allowed to warm slowly to room temperature, stirred under argon for a further 16 h, quenched by pouring into saturated ammonium chloride solution (60 ml) and extracted with diethyl ether (3 * 100 ml). The combined organic extracts are dried MgSO4 and evaporated in vacuo. The (5alpha)-3-[2-(trimethylsilyl)ethylidene]cholestane (3) is isolated column chromatography (Acrus silica gel (0.060-0.200 mm), elution with hexane).
Stage #1: 2-iodobenzophenone With tetramethylurea; zinc at 80℃; for 24h;
Stage #2: iodo(trimethylsilyl)methane With 1,1'-bis-(diphenylphosphino)ferrocene; chloro(1,5-cyclooctadiene)rhodium(I) dimer; tetramethylurea at 40℃; for 12h;
With potassium carbonate; In N,N-dimethyl-formamide; at 60℃; for 21h;
Step A: Iodomethyl trimethylsilane (6.0 ml, 40 mmol) was added to a mixture of <strong>[394-50-3]3-fluorosalicylaldehyde</strong> (5.0 g, 36 mmol) and potassium carbonate (15.2 g, 110 mmol) in dimethylformamide (100 ml). The resulting mixture was heated at 60° C. for 6 hours after which additional iodomethyl trimethylsilane was added. After stirring at 60° C. for 15 hours, the mixture was cooled to room temperature and the solids were removed by filtration. Cesium fluoride (16.4 g, 108 mmol) was added to the filtrate and the resulting mixture was heated at 105° C. for 36 hours. The mixture was extracted with methylene chloride, washed with water and dried over anhydrous magnesium sulfate to give a red/brown oil (3.6 g) which solidified on standing. These crude solids were triturated with hexanes to give light brown needles (2.3 g, 42percent): 1H NMR (500 MHz, DMSO-d6) delta 7.06 (d, J=7.6 Hz, 1H), 7.00 (dd, J=11.4, 8.5 Hz, 1H), 6.75 (ddd, J=12.0, 7.9, 4.4 Hz, 1H), 5.61 (d, J=5.7 Hz, 1H), 5.18 (br s, 1H), 4.46 (dd, J=10.1, 6.9 Hz, 1H), 4.19 (dd, J=10.1, 2.8 Hz, 1H).
With ammonium chloride; In tetrahydrofuran; N,N,N,N,N,N-hexamethylphosphoric triamide; water;
Step A 2-Benzyloxycarbonylamino-3-trimethylsilyl-propanoic acid, methyl ester A solution of 5.58 g (25 mmol) of N-benzyloxycarbonyl glycine methyl ester in dry THF (70 ml) is added dropwise to a solution at -78° C. of lithium diisopropylamine (8.76 ml, 62.5 mmol) and tetramethylethylene diamine (9.43 ml, 62.5 mmol) in dry THF (100 ml), under nitrogen. After the addition is complete, the solution is stirred for 2 hours at -78° C., then 15 minutes at -30° C. and cooled to -78° C. A solution of 5.36 g (25 mmol) of iodomethyl-trimethylsilane in dry hexamethylphosphoramide (39 ml) is added dropwise to the resultant syrupy mixture. After the addition is complete, the reaction mixture is warmed up to -50° C., kept at this temperature for 1 hour and cooled to -78° C., just before hydrolysis. The reaction mixture is quenched by addition of water and ammonium chloride and diluted with ether. The organic layer is washed with 1N potassium hydrogen sulfate, twice with water and dried over sodium sulfate. The solvent is evaporated and the residue obtained (8.03 g) is purified by flash chromatography (silica gel,ethyl acetate/petroleum ether: 2/8). 4.30 g of the title compound are obtained (yield: 56percent) (colorless oil). Rf: 0.51 (ethyl acetate/petroleum ether: 2/8).
methyltrimethylsilyl (R)-2-oxo-1,3-thiazolidine-4-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
54%
With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; for 4h;Product distribution / selectivity;
Example 1: Preparation of methyltrimethylsilyl R-2-oxo- l,3-thiazolidine-4-carboxylate; Route 1 - nucleophilic substitution; Synthetic scheme Procedure 20 g (0.136 mol, 1 eq) of R-2- oxothiazolidine-4-carboxylic acid (sold by the company Nippon Rika) are dissolved in 200 ml of N,N-dimethyl- formamide in a 500 ml three-necked round-bottomed flask equipped with a condenser. 9.4 g of potassium carbonate (0.068 mol, 0.5 eq) are added, followed by addition of 20.2 ml of commercial iodomethyltrimethylsilane (0.136 mol, 1 eq) . This reaction mixture is maintained at 8O0C for 4 hours and is then allowed to cool to room temperature. The insoluble matter of the reaction medium is filtered off on a sinter funnel of porosity 3, and the filtrate is then concentrated under reduced pressure (P = I mbar, T = 400C) . The paste obtained is taken up in 150 ml of ethyl acetate and this organic EPO <DP n="21"/>phase is washed with 3 x 100 ml of water and 100 ml of saturated sodium chloride solution, and is then dried over sodium sulfate and filtered. The solvent is then evaporated under reduced pressure (P = 240 mbar, T = 4O0C) .After purification of this crude product by chromatography on a column of silica, eluting with 8/2 heptane/ethyl acetate, 17.1 g of methyltrimethylsilyl L-2-oxo-l, 3-thiazolidine-4-carboxylate are obtained in wax form. The yield is 54%. The NMR analysis is in accordance with the expected structure.
Stage #1: N-[2-(3,4-dimethoxyphenyl)ethyl]formamide With potassium hexamethylsilazane In tetrahydrofuran; toluene at 20℃; for 1.5h;
Stage #2: iodo(trimethylsilyl)methane In tetrahydrofuran; N,N-dimethyl-formamide; toluene at 20℃; Reflux;
With potassium carbonate In acetone for 18h; Reflux;
Preparation of 2,2,3,3-Tetrafluoro-4-((trimethylsilyl)methoxy)butanol 16.
A mixture of 2,2,3,3-tetrafluoro-1,4-butanediol (1.95 g, 12 mmol), (iodomethyl)trimethylsilane(2.06 g, 9.2 mmol) and anhydrous K2CO3 (5 g, 14.5 mmol)in dry acetone (50 mL) was refluxed for 18 h. The reaction mixture was allowed to cool gradually to ambient temperature. Concentration of solution in vacuo gave a residue which was diluted with diethyl ether and extracted with water. The extracts were dried with Na2SO4, filtered and concentrated in vacuo to afford a residue which was subjected to silica gel column chromatography (1:20 = EtOAc:n-hexane) to afford 16 (1.6 g, 83%).
With potassium carbonate; In acetonitrile; at 20℃; for 12h;
A 100 mL MeCN solution of 50 N,N-bis-ethylcarboxymethylamine (15.5mmol) containing K2CO3 (41.8 mmol) and (iodomethyl)trimethylsilane (20 mmol) was stirred for 12 h at room temperature and concentrated in vacuo to give residue that was in vacuo to afford residues, which were subjected to column chromatography (EtOAc: Hex=1: 8) to yield 10 (69 %).
4-fluoro-N-methyl-N-((trimethylsilyl)methyl)aniline[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
Stage #1: 4-fluoro-N-methylaniline With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 24h; Inert atmosphere;
Stage #2: iodo(trimethylsilyl)methane In tetrahydrofuran; hexane at 20℃; for 12h; Inert atmosphere;
60%
Stage #1: 4-fluoro-N-methylaniline With n-butyllithium In tetrahydrofuran at -78℃; for 1h;
Stage #2: iodo(trimethylsilyl)methane In tetrahydrofuran at -78 - 20℃; for 5h;
4.1.11 Synthesis of α-trimethylsilylamines 78-8038
General procedure: To individual solutions of N-methyl-N-phenylamine derivatives (9.3 mmol) in THF (30 mL) was added n-BuLi (12 mmol) at-78 °C. After stirred for 1 h, (iodomethyl)trimethylsilane (10.3 mmol) was added dropwise to the solutions and the resulting solutions were stirred for 5 h at room temperature. Then, the solutions were quenched by aq. NH4Cl and triturated with CH2Cl2. The triturates were dried and concentrated in vacuo to afford residues, which were subjected to silica gel column chromatography (hexane) to yield 78 (75 %), 79 (44 %) and 80 (60 %).
(4-Methoxy-benzyl)-trimethylsilanylmethyl-amine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
80%
Stage #1: 4-methoxy-benzylamine With potassium carbonate In acetonitrile at 70℃; for 1h; Inert atmosphere;
Stage #2: iodo(trimethylsilyl)methane In acetonitrile at 70℃; for 7h; Inert atmosphere;
General Procedure for Synthesis of Secondary N-Trimethylsilylmethyl-N-benzylamines 6-9
General procedure: The corresponding primary amines 1-4 (1- 5823 mg, 2- 6586 mg, 3- 6801 mg, 4- 7455 mg, 54.35mmol) was taken in acetonitrile (120 mL), added K2CO3 (11266 mg, 81.52 mmol) under argon.The reaction mixture heated at 70 0C for 1 h and iodomethyltrimethylsilane 5 (9697 mg, 45.29mmol) was added dropwise. The reaction mixture stirred for 7 h at 70 0C. After completion ofreaction (checked by TLC), the mixture concentrated in vacuo to give residues that werepartitioned between water and CH2Cl2. The CH2Cl2 layers were dried and concentrated in vacuoto afford residues that were subjected to silica gel column chromatography (EtOAc/hexane = 1:1)to yield the corresponding Secondary N-Trimethylsilylmethyl-N-benzylamines 6 (8197 mg, 78%),7 (9580 mg, 85%), 8 (6317 mg, 55%) and 9 (9712 mg, 80%). The spectral data exactly matchingwith reported one.
63%
With potassium carbonate In acetonitrile at 20℃; for 12h;
α-Silyl benzylamines 42-46
General procedure: Individual solutions of benzylamine derivatives (24.3 mmol of 37 (2.6 g), 28.0 mmol of 38 (3.4 g), 28.0 mmol of 39 (3.8 g), 11.2 mmol of 40 (1.4 g), 11.2 mmol of 41(2.0 g)) in acetonitrile (120 mL) containing K2CO3 (5.2 g (37.4 mmol) for 37, 6.5 g ( 46.7 mmol) for38-39, and 2.6 g (18.7 mmol) for 40-41) and Me3SiCH2I (4.0 g (18.7 mmol) for 37, 5.0 g (23.4 mmol) for 38-39, and 2.0 g (9.3 mmol) for 40-41) were stirred for 12 h at room temperature and concentrated in vacuo to give residues which were triturated with CH2Cl2. The triturates were dried and concentrated in vacuo to afford residues, which were subjected to silica gel column chromatography (EtOAc: hexane = 1: 8 ~ 1: 15) to yield 421 (3.2 g, 89%), 43 (3.85 g, 79%), 442 (3.3g, 63%), 45 (1.51 g, 76 %), and 46 (1.9 g, 78 %).
63%
With potassium carbonate
63%
With potassium carbonate In acetonitrile at 80℃; for 12h;
General procedure for α-aminonitriles 13a-13f.
General procedure: General procedure for α-aminonitriles 13a-13f. Individual MeCN solutions (100 mL) containing primary amines 1-6 (5 mmol), K2CO3 (10 mmol), and (iodomethyl)trimethylsilane (TMSCH2I, 5 mmol) were stirred for 12 h at 80 °C. Then, the reaction solutions were concentrated in vacuo to give residues that were portioned between water and CH2Cl2 layers. The resulting CH2Cl2 layers were dried and concentrated in vacuo to afford residues that were subjected to silica gel column chromatography (EtOAc : Hex = 1:10 - 1:15) to yield corresponding N-(trimethylsilyl)methylsubstituted amines 7 [1] (89 %), 8 [1] (63 %), 9 [1 ] (62 %), 10 [2] (62 %), 11 [2] (64 %), and 12 [2] (73 %). Likewise to above synthetic sequences, MeCN solutions containing 7-12 (5 mmol), K2CO3 (10 mmol) and BrCH2CN (5 mmol) were stirred in 12 h at 80 °C. By using nearly equal work-up condition, all of α-aminonitirles 13a [3] (91 %), 13b [4] (75 %), 13c [4] (78 %), 13d (81 %), 13e (81 %) and 13f (77 %) were successfully prepared.
With potassium carbonate In acetonitrile
With potassium carbonate
Stage #1: 4-methoxy-benzylamine With potassium carbonate In acetonitrile at 70℃; for 1h; Inert atmosphere;
Stage #2: iodo(trimethylsilyl)methane In acetonitrile at 70℃; for 7h; Inert atmosphere;
General procedure forthesynthesis ofsecondary N-trimethylsilylmethyl-N-benzylamines 9-15
General procedure: The corresponding primary amines 1-7 (54.35 mmol) were taken in acetonitrile (120 mL), added K2CO3 (81.52 mmol) under argon. The reaction mixture was heated at 70°C for 1h, and iodomethyltrimethylsilane 8 (45.29mmol) was added dropwise. The reaction mixture stirred for 7h at 70°C. After completion of reaction (checked by TLC), the mixture concentrated in vacuo to give residues that were partitioned between water and CH2Cl2. The CH2Cl2 layers were dried and concentrated in vacuo to aford residues that were subjected to silica gel column chromatography (EtOAc/hexane=1:1) to yield the corresponding secondary N-trimethylsilylmethylN-benzylamines 9-15 (70-88% yields). The spectral data are exactly matched with the reported one.
With potassium carbonate In acetonitrile at 20℃; for 12h;
α-Silyl benzylamines 42-46
General procedure: Individual solutions of benzylamine derivatives (24.3 mmol of 37 (2.6 g), 28.0 mmol of 38 (3.4 g), 28.0 mmol of 39 (3.8 g), 11.2 mmol of 40 (1.4 g), 11.2 mmol of 41(2.0 g)) in acetonitrile (120 mL) containing K2CO3 (5.2 g (37.4 mmol) for 37, 6.5 g ( 46.7 mmol) for38-39, and 2.6 g (18.7 mmol) for 40-41) and Me3SiCH2I (4.0 g (18.7 mmol) for 37, 5.0 g (23.4 mmol) for 38-39, and 2.0 g (9.3 mmol) for 40-41) were stirred for 12 h at room temperature and concentrated in vacuo to give residues which were triturated with CH2Cl2. The triturates were dried and concentrated in vacuo to afford residues, which were subjected to silica gel column chromatography (EtOAc: hexane = 1: 8 ~ 1: 15) to yield 421 (3.2 g, 89%), 43 (3.85 g, 79%), 442 (3.3g, 63%), 45 (1.51 g, 76 %), and 46 (1.9 g, 78 %).
62%
With potassium carbonate
62%
With potassium carbonate In acetonitrile at 80℃; for 12h;
General procedure for α-aminonitriles 13a-13f.
General procedure: General procedure for α-aminonitriles 13a-13f. Individual MeCN solutions (100 mL) containing primary amines 1-6 (5 mmol), K2CO3 (10 mmol), and (iodomethyl)trimethylsilane (TMSCH2I, 5 mmol) were stirred for 12 h at 80 °C. Then, the reaction solutions were concentrated in vacuo to give residues that were portioned between water and CH2Cl2 layers. The resulting CH2Cl2 layers were dried and concentrated in vacuo to afford residues that were subjected to silica gel column chromatography (EtOAc : Hex = 1:10 - 1:15) to yield corresponding N-(trimethylsilyl)methylsubstituted amines 7 [1] (89 %), 8 [1] (63 %), 9 [1 ] (62 %), 10 [2] (62 %), 11 [2] (64 %), and 12 [2] (73 %). Likewise to above synthetic sequences, MeCN solutions containing 7-12 (5 mmol), K2CO3 (10 mmol) and BrCH2CN (5 mmol) were stirred in 12 h at 80 °C. By using nearly equal work-up condition, all of α-aminonitirles 13a [3] (91 %), 13b [4] (75 %), 13c [4] (78 %), 13d (81 %), 13e (81 %) and 13f (77 %) were successfully prepared.
55%
Stage #1: para-fluorobenzylamine With potassium carbonate In acetonitrile at 70℃; for 1h; Inert atmosphere;
Stage #2: iodo(trimethylsilyl)methane In acetonitrile at 70℃; for 7h; Inert atmosphere;
General Procedure for Synthesis of Secondary N-Trimethylsilylmethyl-N-benzylamines 6-9
General procedure: The corresponding primary amines 1-4 (1- 5823 mg, 2- 6586 mg, 3- 6801 mg, 4- 7455 mg, 54.35mmol) was taken in acetonitrile (120 mL), added K2CO3 (11266 mg, 81.52 mmol) under argon.The reaction mixture heated at 70 0C for 1 h and iodomethyltrimethylsilane 5 (9697 mg, 45.29mmol) was added dropwise. The reaction mixture stirred for 7 h at 70 0C. After completion ofreaction (checked by TLC), the mixture concentrated in vacuo to give residues that werepartitioned between water and CH2Cl2. The CH2Cl2 layers were dried and concentrated in vacuoto afford residues that were subjected to silica gel column chromatography (EtOAc/hexane = 1:1)to yield the corresponding Secondary N-Trimethylsilylmethyl-N-benzylamines 6 (8197 mg, 78%),7 (9580 mg, 85%), 8 (6317 mg, 55%) and 9 (9712 mg, 80%). The spectral data exactly matchingwith reported one.
With potassium carbonate In acetonitrile
With potassium carbonate
Stage #1: para-fluorobenzylamine With potassium carbonate In acetonitrile at 70℃; for 1h; Inert atmosphere;
Stage #2: iodo(trimethylsilyl)methane In acetonitrile at 70℃; for 7h; Inert atmosphere;
General procedure forthesynthesis ofsecondary N-trimethylsilylmethyl-N-benzylamines 9-15
General procedure: The corresponding primary amines 1-7 (54.35 mmol) were taken in acetonitrile (120 mL), added K2CO3 (81.52 mmol) under argon. The reaction mixture was heated at 70°C for 1h, and iodomethyltrimethylsilane 8 (45.29mmol) was added dropwise. The reaction mixture stirred for 7h at 70°C. After completion of reaction (checked by TLC), the mixture concentrated in vacuo to give residues that were partitioned between water and CH2Cl2. The CH2Cl2 layers were dried and concentrated in vacuo to aford residues that were subjected to silica gel column chromatography (EtOAc/hexane=1:1) to yield the corresponding secondary N-trimethylsilylmethylN-benzylamines 9-15 (70-88% yields). The spectral data are exactly matched with the reported one.
With n-butyllithium; In tetrahydrofuran; hexane; at 0 - 20℃;Inert atmosphere;
General procedure: Typical procedure: A hexane solution of butyllithium (1.65 M,5.57 mL, 9.2 mmol) was added dropwise to a THF (10 mL) solutionof <strong>[3561-67-9]bis(phenylthio)methane</strong> (1.859 g, 8.0 mmol) at 0 C over 30 min.After stirring for 1 h, (iodomethyl)trimethylsilane (1.37 mL,9.2 mmol)was added dropwise over 15 min at 0 C and the reactionmixturewas graduallywarmed up to room temperature and stirredovernight. The reactionwas quenched by addition of water (30 mL)and the organic materials were extracted with ether (30 mL3) anddried over Na2SO4. After removal of solvent, the residue was purifiedby silica gel column chromatography (hexane/AcOEt98:2) togive 6a (1.87 g, 73%). In a similar manner, the silyl thioacetals 6b(52%) and 6c (41%) were obtained using benzyl(iodomethyl)dimethylsilaneand (iodomethyl)dimethylphenylsilane, respectively.
4-cyano-N-[(trimethylsilyl)methyl]benzamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
Stage #1: 4-cyanobenzamide With sodium hydride In N,N-dimethyl-formamide; mineral oil at 20℃; for 2h; Inert atmosphere;
Stage #2: iodo(trimethylsilyl)methane In N,N-dimethyl-formamide; mineral oil at 60℃; for 24h; Inert atmosphere;
With potassium carbonate; In acetonitrile; at 80℃; for 12h;
General procedure: General procedure for alpha-aminonitriles 13a-13f. Individual MeCN solutions (100 mL) containing primary amines 1-6 (5 mmol), K2CO3 (10 mmol), and (iodomethyl)trimethylsilane (TMSCH2I, 5 mmol) were stirred for 12 h at 80 C. Then, the reaction solutions were concentrated in vacuo to give residues that were portioned between water and CH2Cl2 layers. The resulting CH2Cl2 layers were dried and concentrated in vacuo to afford residues that were subjected to silica gel column chromatography (EtOAc : Hex = 1:10 - 1:15) to yield corresponding N-(trimethylsilyl)methylsubstituted amines 7 [1] (89 %), 8 [1] (63 %), 9 [1 ] (62 %), 10 [2] (62 %), 11 [2] (64 %), and 12 [2] (73 %). Likewise to above synthetic sequences, MeCN solutions containing 7-12 (5 mmol), K2CO3 (10 mmol) and BrCH2CN (5 mmol) were stirred in 12 h at 80 C. By using nearly equal work-up condition, all of alpha-aminonitirles 13a [3] (91 %), 13b [4] (75 %), 13c [4] (78 %), 13d (81 %), 13e (81 %) and 13f (77 %) were successfully prepared.
With palladium diacetate; caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene In benzene at 20℃; for 12h; Inert atmosphere; Glovebox; Irradiation; Sealed tube; Schlenk technique;
(3-(4-bromo-2-methylphenyl)allyl)trimethylsilane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81.8%
To a solution of PhsPCFpBr (65 g, 182 mmol) in THF (200 mL) was added nBuLi (80.5 mL, 201.3 mmol. 2.5 M in hexane) at 0C. The resulting solution was warmed and stirred at 25C for 1 h. The solution was cooled to 0C and a solution of TMS-CFLI (47 g, 219.5 mmol) in THF (200 mL) was added. The reaction mixture was stirred at 25C for 24 h. The reaction mixture was cooled to 0C and a solution of nBuLi (66.5 mL, 166.3 mmol, 2.5 M in hexane) was added. The reaction mixture was kept at 0C for 1 h, then cooled to -78C . 4-Bromo-2- methylbenzaldehyde (30 g, 150.7 mmol) was added at -78C, then reaction mixture was warmed to room temperature and stirred for 3 h. Upon completion, the reaction was quenched with aq. MLCl (200 mL). The organic layer was separated. The aqueous phase was extracted with ethyl acetate (150 mL x 3). The combined organic layers were washed with brine (200 mL), dried over NaiSCL, and concentrated in vacuo. The residue was purified by column chromatography on silica gel using petroleum ether as eluent to afford title product (34.9 g, 81.8% yield, mixture of isomers) as a colorless oil. ESI-MS [M+H]+Calc’d for(Ci3Hi9BrSiH+) 283.25, found, No Mass.