Stereochemical Course of Deprotonation-Acylation of N-Boc- and N-Carbamoyl-2-cyano-6-methylpiperidines

• Kotomori, Yuri

• Sasaki, Michiko

• Kawahata, Masatoshi

• Yamaguchi, Kentaro

• Takeda, Kei

Bibliographic Information

Other Title

• Stereochemical Course of Deprotonation-Acylation of <i>N</i>-Boc- and <i>N</i>-Carbamoyl-2-cyano-6-methylpiperidines

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.

Journal

• The Journal of Organic Chemistry

  The Journal of Organic Chemistry 80 (21), 11013-11020, 2015-11-06

  American Chemical Society

Keywords

• Organic Chemistry

Details

• CRID: 1050859215938502016
• NII Article ID: 120005774708
• DOI: 10.1021/acs.joc.5b02178
• ISSN: 15206904
• ISSN: 00223263
• Web Site: http://ir.lib.hiroshima-u.ac.jp/00040588
• Web Site: https://pubs.acs.org/doi/pdf/10.1021/acs.joc.5b02178
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • Crossref
  • CiNii Articles
  • KAKEN