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S N i fragmentations of alkoxychlorocarbenes – a perspective
Author(s) -
Moss Robert A.,
Fu Xiaolin,
Sauers Ronald R.
Publication year - 2007
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.1121
Subject(s) - chemistry , alkyl , counterion , computational chemistry , perspective (graphical) , solvent , transition state , solvent polarity , stereochemistry , ion , medicinal chemistry , organic chemistry , catalysis , artificial intelligence , computer science
After a review of the early literature concerning S N i fragmentations of alkyl chlorosulfites and chloroformates, we present experimental and computational results for the S N i fragmentations of alkoxychlorocarbenes. Examples include cyclohexyloxychlorocarbene, 7‐norbornyloxychlorocarbene, 3‐nortricyclyloxychlorocarbene, exo ‐5‐norbornenyl‐2‐oxychlorocarbene, and endo ‐5‐norbornenyl‐2‐oxychlorocarbene. Computations generate a ‘family’ of closely related charge‐separated S N i structures which approximate asynchronous, polar, concerted transition states and tight, short‐lived ion pair intermediates. The precise description and behavior of these species in a given reaction depends on the identities of the alkyl group, the potential counterion, and the solvent. Copyright © 2007 John Wiley & Sons, Ltd.