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ID 40588
file
creator
Kotomori, Yuri
Kawahata, Masatoshi
Yamaguchi, Kentaro
NDC
Medical sciences
abstract
The stereochemical course of electrophilic substitution of α-nitrile metallocarbanions generated by deprotonation from N-Boc- and N-carbamoyl-2-cyano-6-methylpiperidines was investigated. Deprotonation in the presence of an electrophile taking advantage of the high acidity of α-nitrile protons allowed examination of the effects of a chelating group on the nitrogen atom, a countercation, and the reactivity of an electrophile on the steric course. Analyses of reactions using aroyl chlorides and methyl iodide revealed the following: (1) the substitution reactions basically proceed with retention of configuration, (2) the extent of an inversion product increases with decreasing chelating ability of the N-substituent and with increasing leaving ability (ionic character) of a countercation (Li, Na, K) of the anionic species, and (3) the use of a more reactive electrophile results in an increase of the retention product.
description
This research was partially supported by a Grant-in-Aid for Scientific Research (C) 25460015 (M.S.) a Grant-in-Aid for Scientific Research (B) 22390001 (K.T.), a Grant-in-Aid for Challenging Exploratory Research 23659007 (K.T.) and 15K14929 (K.T.) from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), the Hoansha Foundation (M.S.), the Takeda Science Foundation (M.S.) and the Naito Foundation Natural Science Scholarship (M.S.).
journal title
The Journal of Organic Chemistry
volume
Volume 80
issue
Issue 21
start page
11013
end page
11020
date of issued
2015-11-06
publisher
American Chemical Society
issn
0022-3263
publisher doi
pubmed id
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
publisher
rights
Copyright (c) 2015 American Chemical Society
This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
relation is version of
http://doi.org/10.1021/acs.joc.5b02178
department
Graduate School of Biomedical & Health Sciences



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