Aziridines. 59. Regioselectivity in nucleophilic Ring Opening of 2‐Methylaziridines. Lag of bond making as model for the abnormal opening

Pen‐Yuan ‐Y Lin, Gunther Bentz, H. Stamm

研究成果: 雜誌貢獻文章同行評審

18 引文 斯高帕斯(Scopus)

摘要

The regioselectivity ratio RS = normal: abnormal opening of activated 2‐methylaziridines 2 by nucleophiles is found to range from 0.10 to unmeasurable large (only normal opening = substitution at CH2 by strongly basic carbanions). RS is assumed to result from SN2 variants differing in the degree to which bond breaking is ahead of bond making including perhaps synchronous SN2. Bond breaking will be more ahead for the N‐CMe bond. High nucleophilic power pushes bond making toward a synchronous process resulting in great RS. The decrease in RS with acyl activation relative to sulfonyl activation is in accord with a flattening of the nitrogen pyramid (planarization effect). The planarization effect is retained in acidic medium by O‐protonation: Rs 0.10–0.14 for methanolysis as compared to RS 0.43 for N‐protonated sulfonylaziridine 2h. AM1 calculations support the planarization hypothesis. – No indication for SET with trityl anion was found.

原文英語
頁(從 - 到)23-34
頁數12
期刊Advanced Synthesis and Catalysis
335
發行號1
DOIs
出版狀態已發佈 - 1993
對外發佈

ASJC Scopus subject areas

  • 催化
  • 有機化學

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