869218-56-4

Basic information

• Product Name: (R,R)-1,2-dicyclohexylethane-1,2-diol (1S)-(dimethylphenylsilyl)-[1-2H]methylboronate
• Synonyms: (R,R)-1,2-dicyclohexylethane-1,2-diol (1S)-(dimethylphenylsilyl)-[1-2H]methylboronate
• CAS NO: 869218-56-4
• Molecular Weight: 385.434
• Mol File: 869218-56-4.mol
• Article Data: 3

Chemical Properties

• CAS DataBase Reference: (R,R)-1,2-dicyclohexylethane-1,2-diol (1S)-(dimethylphenylsilyl)-[1-2H]methylboronate(CAS DataBase Reference)
• NIST Chemistry Reference: (R,R)-1,2-dicyclohexylethane-1,2-diol (1S)-(dimethylphenylsilyl)-[1-2H]methylboronate(869218-56-4)
• EPA Substance Registry System: (R,R)-1,2-dicyclohexylethane-1,2-diol (1S)-(dimethylphenylsilyl)-[1-2H]methylboronate(869218-56-4)

Safety Data

• Hazardous Substances Data: 869218-56-4(Hazardous Substances Data)

Upstream product

• 1051943-06-6 C₃₃H₅₃⁽²⁾HBNO₄Si 
• 1051943-00-0 C₃₃H₅₄BNO₄Si 
• 869218-53-1 (R,R)-1,2-dicyclohexylethane-1,2-diol {(1S)-[(S,S)-N,N-bis(1-phenylethyl)carbamoyloxy](dimethylphenylsilyl)methyl}boronate 
• 120850-92-2 (1R,2R)-1,2-dicyclohexyl-1,2-ethanediol 
• 5584-87-2 (dimethylphenylsilyl)methyl acetate 
• 1833-51-8 chloromethyldimethylphenylsilane 
• 17881-97-9 (hydroxymethyl)dimethylphenylsilane 
• 869218-44-0 (dimethylphenylsilyl)methyl (S,S)-N,N-bis(1-phenylethyl)carbamate 
• 869218-63-3 (S)-pinanediol (dimethylphenylsilyl)methylboronate 
• 869218-52-0 (R,R)-1,2-dicyclohexylethane-1,2-diol tert-butyl alcohol borate 

Downstream Products

• 869218-58-6 (S)-(dimethyl(phenyl)silyl)-[1-D₁]methanol 

Relevant articles and documents

Formal and improved synthesis of enantiopure chiral methanol

[D2]Methanol was converted to the carbamate derived from 2,2,6,6-tetramethylpiperidine. It was metalated with s-BuLi/TMEDA at -78 °C with a high primary kinetic isotope effect to give an α-oxymethyllithium, which was silylated with chlorodimethylphenylsilane. The silylmethyl carbamate formed was lithiated and borylated with the borate derived from tert-butanol and (R,R)-1,2-dicyclohexylethane-1,2-diol to give diastereomeric boronates, which were separated by preparative HPLC and can in principle be converted to enantiopure chiral methanols. Thus, both enantiomers are easily accessible in nine linear steps.

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%).