Stereochemical Course of Deprotonation-Acylation of N-Boc- and N-Carbamoyl-2-cyano-6-methylpiperidines
The Journal of Organic Chemistry 80 巻 21 号
11013-11020 頁
2015-11-06 発行
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| ファイル情報(添付) | |
| タイトル ( eng ) |
Stereochemical Course of Deprotonation-Acylation of N-Boc- and N-Carbamoyl-2-cyano-6-methylpiperidines
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| 作成者 |
Kotomori Yuri
Kawahata Masatoshi
Yamaguchi Kentaro
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| 収録物名 |
The Journal of Organic Chemistry
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| 巻 | 80 |
| 号 | 21 |
| 開始ページ | 11013 |
| 終了ページ | 11020 |
| 抄録 |
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.
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| 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.).
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| NDC分類 |
医学 [ 490 ]
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| 言語 |
英語
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| 資源タイプ | 学術雑誌論文 |
| 出版者 |
American Chemical Society
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| 発行日 | 2015-11-06 |
| 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.
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| 出版タイプ | Version of Record（出版社版。早期公開を含む） |
| アクセス権 | オープンアクセス |
| 収録物識別子 |
http://doi.org/10.1021/acs.joc.5b02178
～の異版である
[ISSN] 0022-3263
[DOI] 10.1021/acs.joc.5b02178
[PMID] 26457453
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