Tris(propan-2-yl)silanethiol → Methyl-(2-triisopropylsilanylsulfanyl-benzyl)-carbamic acid tert-butyl ester

HRID 16637

Reaction equation

HRID 16637 reaction equation
[C:1]([O:5][C:6](=[O:17])[N:7]([CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1I)[CH3:8])([CH3:4])([CH3:3])[CH3:2].[CH:18]([Si:21]([CH:26]([CH3:28])[CH3:27])([CH:23]([CH3:25])[CH3:24])[SH:22])([CH3:20])[CH3:19].CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2OC2C=CC=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[C:1]([O:5][C:6](=[O:17])[N:7]([CH3:8])[CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[S:22][Si:21]([CH:23]([CH3:25])[CH3:24])([CH:26]([CH3:28])[CH3:27])[CH:18]([CH3:19])[CH3:20])([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 3

HCID 3435097Tris(propan-2-yl)silanethiolHCID 23676156Sodium t-butoxideHCID 67018447tert-Butyl 2-iodobenzyl(methyl)carbamate

Product 1

HCID 67018449Methyl-(2-triisopropylsilanylsulfanyl-benzyl)-carbamic acid tert-butyl esterYield 167.9%

Reagents, catalysts & solvents 3

HCID 4285986Bis[2-(diphenylphosphino)phenyl] etherCatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
160 °C

Procedure

(2-Iodo-benzyl)-methyl-carbamic acid tert-butyl ester (5.0 g, 14.4 mmol) in dry toluene (30 mL) was placed in two Emrys Optimizer EXP 20 mL tubes. To each tube tris(dibenzylideneacetone)dipalladium (66 mg, 0.072 mmol), bis(2-diphenylphosphinophenyl)ether (78 mg, 0.14 mmol), triisopropylsilanethiol (1.44 g, 7.56 mmol) and sodium tert-butoxide (900 mg, 9.36 mmol) were added sequentially. The tubes were sealed and subjected to microwave heating at 160° C. for 15 minutes. After cooling the mixture, the product was eluted through a plug of silica with ethyl acetate-heptane (1:10) to give 5.2 g (88%) of methyl-(2-triisopropylsilanylsulfanyl-benzyl)-carbamic acid tert-butyl ester. This product was dissolved in THF (70 mL) and cooled to 0° C. Tetrabutylammonium fluoride trihydrate (4.21 g, 13.3 mmol) dissolved in THF (40 mL) was added dropwise at 0° C. and the mixture was stirred at this temperature for 15 minutes. The crude mixture was poured onto a plug of silica gel and the product was eluted with ethyl acetate-heptane (1:2) to give 3.2 g (100%) of (2-mercapto-benzyl)-methyl-carbamic acid tert-butyl ester contaminated with traces of triisopropylsilane fluoride.

Workup

  1. customThe tubes were sealed
  2. temperatureAfter cooling the mixture
  3. washthe product was eluted through a plug of silica with ethyl acetate-heptane (1:10)

Sources & evidence

ORD record
ord-50af742b06424be395122fb7df0c8b76
Source dataset
uspto-grants-2010_06
Patent number
US07737171B2

Linked notes

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