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Synthesis 2021; 53(24): 4700-4708
DOI: 10.1055/a-1528-8357
paper

Methylation Alkynylation of Terminal Alkenes via 1,2-Alkynyl Migration Using Dicumyl Peroxide as the Methyl Source

Yi-qun Qin
a   Advanced Catalytic Engineer Research Center of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
,
De Chen
a   Advanced Catalytic Engineer Research Center of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
,
Liang Liu
a   Advanced Catalytic Engineer Research Center of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
,
Jia-jia Zhang
a   Advanced Catalytic Engineer Research Center of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
,
Xin-ju Peng
a   Advanced Catalytic Engineer Research Center of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
,
Yong-yue Luo∗
b   Agricultural Product Processing Research Institute, Chinese Academy of Tropical Agricultural Sciences, Zhanjiang 440800, P. R. of China
,
Wei Deng∗
a   Advanced Catalytic Engineer Research Center of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
,
Jiannan Xiang∗
a   Advanced Catalytic Engineer Research Center of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. of China
› Author AffiliationsWe are grateful for financial support from the National Natural Science­ Foundation of China (No. 21502049 and 51573040) and the Natural Science Foundation of Hunan Province (No. 2018JJ2032).
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Abstract

The metal-free oxidative alkene methylation/alkynylation of 1,4-enyn-3-ols with an organic peroxide as the methyl source has been developed, which provides straightforward and practical access to the challenging quaternary-carbon-containing but-3-yn-1-ones. The method is reasoned to go through methylation of functional alkenes utilizing dicumyl peroxide as the methylating reagent and subsequent intermolecular cyclization/1,2-alkynyl migration. This reaction has an excellent functional group tolerance, broad substrate scope, and exquisite selectivity.

Key words

alkene difunctionalization - migration reaction - radical

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1528-8357.
  • Supporting Information


Publication History

Received: 08 May 2021

Accepted after revision: 15 June 2021

Accepted Manuscript online:
15 June 2021

Article published online:
23 August 2021

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