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ID 40588
本文ファイル
著者
Kotomori, Yuri
Kawahata, Masatoshi
Yamaguchi, Kentaro
NDC
医学
抄録(英)
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.
内容記述
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.).
掲載誌名
The Journal of Organic Chemistry
80巻
21号
開始ページ
11013
終了ページ
11020
出版年月日
2015-11-06
出版者
American Chemical Society
ISSN
0022-3263
出版者DOI
PubMedID
言語
英語
NII資源タイプ
学術雑誌論文
広大資料タイプ
学術雑誌論文
DCMIタイプ
text
フォーマット
application/pdf
著者版フラグ
publisher
権利情報
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.
関連情報(IsVersionOf)
http://doi.org/10.1021/acs.joc.5b02178
部局名
医歯薬保健学研究科