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Furanosyl Oxocarbenium Ion Stability and Stereoselectivity
Author(s) -
van Rijssel Erwin R.,
van Delft Pieter,
Lodder Gerrit,
Overkleeft Herman S.,
van der Marel Gijsbert A.,
Filippov Dmitri V.,
Codée Jeroen D. C.
Publication year - 2014
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201405477
Subject(s) - oxocarbenium , stereoselectivity , triethylsilane , chemistry , anomeric effect , nucleophile , stereochemistry , arabinose , computational chemistry , lewis acids and bases , ion , anomer , xylose , organic chemistry , catalysis , fermentation
Lewis acid mediated substitution reactions using [D]triethylsilane as a nucleophile at the anomeric center of the four pentofuranoses, ribose, arabinose, xylose, and lyxose, all proceed with good to excellent stereoselectivity to provide the 1,2‐ cis adducts. To unravel the stereoelectronic effects underlying the striking stereoselectivity in these reactions we have mapped the energy landscapes of the complete conformational space of the oxocarbenium ions of the four pentofuranoses. The potential energy surface maps provide a detailed picture of the influence of the differently oriented substituents and their mutual interactions on the stability of the oxocarbenium ions and the maps can be used to account for the observed stereoselectivities of the addition reactions.