819816-70-1

Basic information

• Product Name: (S)-pinanediol {(1R)-[(R,R)-N,N-bis(1-phenylethyl)carbamoyloxy](trimethylsilyl)methyl}boronate
• Synonyms: (S)-pinanediol {(1R)-[(R,R)-N,N-bis(1-phenylethyl)carbamoyloxy](trimethylsilyl)methyl}boronate
• CAS NO: 819816-70-1
• Molecular Weight: 533.591
• Mol File: 819816-70-1.mol
• Article Data: 2

Chemical Properties

• CAS DataBase Reference: (S)-pinanediol {(1R)-[(R,R)-N,N-bis(1-phenylethyl)carbamoyloxy](trimethylsilyl)methyl}boronate(CAS DataBase Reference)
• NIST Chemistry Reference: (S)-pinanediol {(1R)-[(R,R)-N,N-bis(1-phenylethyl)carbamoyloxy](trimethylsilyl)methyl}boronate(819816-70-1)
• EPA Substance Registry System: (S)-pinanediol {(1R)-[(R,R)-N,N-bis(1-phenylethyl)carbamoyloxy](trimethylsilyl)methyl}boronate(819816-70-1)

Safety Data

• Hazardous Substances Data: 819816-70-1(Hazardous Substances Data)

Upstream product

• 600728-20-9 Bis-((R)-1-phenyl-ethyl)-carbamic acid trichloromethyl ester 
• 10024-74-5 (R,R)-N,N-bis-(1-phenylethyl)amine 
• 18680-27-8 pinanediol 
• 819816-63-2 (R,R)-(+)-(trimethylsilyl)methyl N,N-bis(1-phenylethyl)carbamate 
• 819816-60-9 (S)-pinane-2,3-diol tert-butyl alcohol borate 
• 819816-59-6 (3aS,4s,6S,7aR)-hexahydro-3a,5,5-trimethyl-2-(1-methylethoxy)-4,6-methano-1,3,2-benzodioxaborole 

Relevant articles and documents

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%).