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Chinese Journal of Organic Chemistry >

2021 , Vol. 41 >Issue 6: 2408 - 2416

DOI: https://doi.org/10.6023/cjoc202101042

ARTICLES

Study on tert-Butyl Radical-Initiated 1,2-Alkynyl Migration

  • Ping Zhang ,
  • Tianshu Zhang ,
  • Peijun Cai ,
  • Bo Jiang ,
  • Shujiang Tu
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  • a School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou, Jiangsu 221116
    b School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116
    c Jiangsu Provincial Xuzhou Pharmaceutical Vocational College, Xuzhou, Jiangsu 221116
*Corresponding authors.E-mail:;

Received date: 2021-01-26

  Revised date: 2021-02-12

  Online published: 2021-02-26

Supported by

Fundamental Research Funds for the Central Universities(JH180263)

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Abstract

A new tert-butyl radical-induced 1,2-alkynyl migration reaction is reported. By using the characteristics of in-situ-generation of tert-butyl radical from pivalaldehyde mediated by di-tert-butyl peroxide (DTBP), tert-butyl radical-triggered addition and alkynyl migration of the preformed 1,4-enynes led to the synthesis of a series of α-alkynyl ketones with good to excellent yields, thereby realizing alkylalkynylation of unactivated olefins. Based on the experimental results and literature reports, a possible reaction mechanism is proposed, which involvestert-butyl radical-triggered addition, 3-exo-dig cyclization of anti-“Baldwin” rule and alkynyl migration process. This reaction has the advantages of high functional group compatibility, metal-free conditions, and simple operation, which provides a feasible and effective synthetic strategy for the bifunctionalization of unactivated olefins.

Key words： alkynyl migration; 1,4-enynes; bifunctionalization; anti-baldwin rule

Cite this article

Ping Zhang , Tianshu Zhang , Peijun Cai , Bo Jiang , Shujiang Tu . Study on tert-Butyl Radical-Initiated 1,2-Alkynyl Migration[J]. Chinese Journal of Organic Chemistry, 2021 , 41(6) : 2408 -2416 . DOI: 10.6023/cjoc202101042

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