869218-46-2

Upstream product

• 869218-41-7 (dimethylphenylsilyl)methyl N,N-dimethylcarbamate 
• 819816-60-9 (S)-pinane-2,3-diol tert-butyl alcohol borate 
• 5584-87-2 (dimethylphenylsilyl)methyl acetate 
• 1833-51-8 chloromethyldimethylphenylsilane 
• 17881-97-9 (hydroxymethyl)dimethylphenylsilane 
• 869218-53-1 (R,R)-1,2-dicyclohexylethane-1,2-diol {(1S)-[(S,S)-N,N-bis(1-phenylethyl)carbamoyloxy](dimethylphenylsilyl)methyl}boronate 
• 869218-55-3 (R,R)-1,2-dicyclohexylethane-1,2-diol (dimethylphenylsilyl)methylboronate 
• 869218-44-0 (dimethylphenylsilyl)methyl (S,S)-N,N-bis(1-phenylethyl)carbamate 
• 869218-63-3 (S)-pinanediol (dimethylphenylsilyl)methylboronate 
• 869218-54-2 (R,R)-1,2-dicyclohexylethane-1,2-diol {(R)-[(S,S)-N,N-bis(1-phenylethyl)carbamoyloxy](dimethylphenylsilyl)methyl}boronate 

Downstream Products

• 869218-59-7 (R)-(dimethyl(phenyl)silyl)-[1-D₁]methanol 
• 869218-64-4 (S)-pinanediol (1R)-(dimethylphenylsilyl)-[1-2H]methylboronate 

Relevant academic research and scientific papers

Direct chemical synthesis of chiral methanol of 98% ee and its conversion to [2H1,3H]methyl tosylate and [ 2H1,3H-methyl]methionine

This paper describes the synthesis of chiral methanols [(R)- and (S)-CHDTOH] in a total of 12 steps starting from (chloromethyl) dimethylphenylsilane. The metalated carbamates derived from (dimethylphenylsilyl)methanol and secondary amines were borylated at low temperatures (-78 or -94°C) using borates derived from fert-butyl alcohol and (+)-pinane-2,3-diol or (R,R)-1,2-dicyclohexylethane-1,2-diol to give diastereomeric boronates (dr 1:1 to 5:1). The carbamoyloxy group could be replaced smoothly with inversion of configuration by an isotope of hydrogen using LiAIH(D)4 [or LiBEt3H(D,T)]. If the individual diastereomeric boronates were reduced with LiAID4 and oxidized with H2O2/NaHCO3, monodeuterated (dimethylphenylsilyl)methanols of ee > 98% resulted. The absolute configurations of the boronates were based on a single-crystal X-ray structure analysis. Brook rearrangement of the enantiomers of (dimethylphenylsilyl)-[ 2H1,3H]methanol prepared similarly furnished the chiral methanols which were isolated as 3,5-dinitrobenzoates in 81% and 90% yield, respectively. For determination of the enantiomeric excesses (98%), the methyl groups were transferred to the nitrogen of (S)-2-methylpiperidine and 3H{1H} NMR spectra were recorded. The Brook rearrangement is a stereospecific process following a retentive course. The chiral methanols were also transformed into methyl tosylates used to prepare [2H 1,3H-methyl]methionines in high overall yields (>80%).