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Diastereoselective Osmium‐catalyzed Vicinal Oxyamination of Acyclic Allylic Alcohol Derivatives
Author(s) -
Kanizaj Nicholas,
McLeod Malcolm D.
Publication year - 2014
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.22256
Subject(s) - chemistry , allylic rearrangement , stereocenter , osmium , double bond , regioselectivity , dihydroxylation , stereoselectivity , substituent , medicinal chemistry , vicinal , chirality (physics) , reactivity (psychology) , stereochemistry , alcohol , catalysis , organic chemistry , enantioselective synthesis , ruthenium , medicine , chiral symmetry breaking , physics , alternative medicine , pathology , quantum mechanics , quark , nambu–jona lasinio model
The osmium‐catalyzed oxyamination of chiral acyclic allylic alcohol derivatives bearing mono‐ and 1,1‐di‐substituted double bonds with benzyl N ‐(4‐tosyloxy)carbamate proceeds with high regioselectivity and moderate levels of diastereoselectivity favoring the anti product. The observed stereoselectivity shows a clear and systematic trend with anti : syn ratios increasing in line with the size of substituent at both the allylic stereocenter and double bond α‐carbon. The stereoinduction is in accord with the sense of diastereoselectivity predicted by Kishi's empirical rule and a previously reported transition state model for the osmium‐catalyzed dihydroxylation of allylic alcohol derivatives. In contrast, allylic alcohol derivatives bearing trisubstituted double bonds show low or no reactivity in the oxyamination reaction affording the syn product in low yield in the cases examined. Chirality 26:724–733, 2013 . © 2013 Wiley Periodicals, Inc.