SYNTHESIS OF ASYMMETRICALLY DEUTERATED GLYCEROL AND DIBENZYLGLYCERALDEHYDE VIA BORONIC ESTERS

(S)-Pinanediol [(benzyloxy)methyl]boronate (1a) has been converted via an improved procedure to (S)-pinanediol (1R)-[1,2-bis(benzyloxy)ethyl]boronate (3a) (96% de), which with (dibromomethyl)lithium has yielded (S)-pinanediol (1S,2S)-[2,3-(benzyloxy)-1-bromopropyl]boronate (4Da). Treatment with pota...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 112; no. 10; pp. 3964 - 3969
Main Authors MATTESON, DS, KANDIL, AA, SOUNDARARAJAN, R
Format Journal Article
LanguageEnglish
Published WASHINGTON Amer Chemical Soc 09.05.1990
American Chemical Society
Subjects
Aliphatic compounds
Chemistry
Chemistry, Multidisciplinary
Exact sciences and technology
Organic chemistry
Physical Sciences
Preparations and properties
Science & Technology
Deuterium
Aldose
Isotope labelling
Asymmetric synthesis
Aliphatic compound
Saturated compound
Boron Organic compounds
Oxygen boron heterocycle
Hydrogen Isotopes
Tricyclic compound
Triol
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Summary:(S)-Pinanediol [(benzyloxy)methyl]boronate (1a) has been converted via an improved procedure to (S)-pinanediol (1R)-[1,2-bis(benzyloxy)ethyl]boronate (3a) (96% de), which with (dibromomethyl)lithium has yielded (S)-pinanediol (1S,2S)-[2,3-(benzyloxy)-1-bromopropyl]boronate (4Da). Treatment with potassium triisopropoxyborodeuteride has yielded (S)-pinanediol (1R,2R)-[2,3-bis(benzyloxy)propyl]boronate-1-d (5Da), which on deboronation with hydrogen peroxide and debenzylation has yielded (1S,2S)-glycerol-1-d (7D) in .apprx. 92-94% de. The opposite diastereomer, (1R,2S)-glycerol-1-d (7L), was obtained via 3a with (dibromomethyl)lithium-d and reduction of the resulting (S)-pinanediol (1S,2R)-[2,3-bis(benzyloxy)propyl]boronate-1-d (5La) with lithium triethylborohydride. Chain extension of (S)-pinanediol (p-methoxybenzyl)boronate (1b) via the alcohols 6b, benzylation to 8b, and DDQ cleavage of the methoxybenzyl group to form alcohols 8c followed by Swern oxidation has led to dibenzyl-(2R,3S)-glyceraldehyde-3-d (9D) and dibenzyl-(2R,3R)-glyceraldehyde-3-d (9L). Conversion of 8c to the crystalline trityl ether 8d reveals that deuterium label placement is in .gtoreq.98% absolute configurational excess, and the major diastereomeric contaminant (2-3%) of the glycerol-d is in error at C(2).
ISSN:0002-7863
1520-5126
DOI:10.1021/ja00166a037