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Steric Considerations on Improving the Diastereomeric Ratio of (+)‐ and (−)‐Neomenthyl Phenyl Sulfoxides Using Bulky‐Headed Oxidant Hexadecyltrimethylammonium Periodate and Assignment of Their Configuration
Author(s) -
Chaudhari Umesh V.,
Singh Deepak,
Deota Pradeep T.,
Bedekar Ashutosh V.
Publication year - 2015
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.22454
Subject(s) - diastereomer , chemistry , sulfoxide , steric effects , periodate , sodium periodate , stereochemistry , absolute configuration , medicinal chemistry , organic chemistry
The bulky‐headed oxidant hexadecyltrimethylammonium periodate affords the diastereomeric pairs, ( Ss )‐(+)/( Rs )‐(+) and ( Ss )‐(−)/( Rs )‐(−)‐neomenthyl phenyl sulfoxides in stereochemically pure states with improved diastereomeric excess (48% diastereomeric excess [de]) as compared to its nonbulky counterpart, sodium metaperiodate (28% de) from respective (+)/(−)‐neomenthyl phenyl sulfides. Steric effects involving the head group volume of hexadecyltrimethylammonium periodate is found to play a role in improving the diastereomeric ratio of the products. The two diastereomers can be readily separated by column chromatography. Absolute configuration at the sulfur center in (+)‐neomenthyl phenyl sulfoxide was determined by single‐crystal X‐ray crystallography and found to be Ss . Relative configurations of other sulfoxides were assigned based on the configuration of (+)‐neomenthyl phenyl sulfoxide. Chirality 27:370–374, 2015 . © 2015 Wiley Periodicals, Inc.