Nucleophilic Migratory Cyclopropenation of Activated Alkynes: A Nonmetal Approach to Unbiased Cyclopropenes

Pengwei Tan; Haoran Wang; Sunewang R Wang

doi:10.1021/acs.orglett.1c00498

Nucleophilic Migratory Cyclopropenation of Activated Alkynes: A Nonmetal Approach to Unbiased Cyclopropenes

Org Lett. 2021 Apr 2;23(7):2590-2594. doi: 10.1021/acs.orglett.1c00498. Epub 2021 Mar 23.

Authors

Pengwei Tan¹, Haoran Wang¹, Sunewang R Wang^{1

2}

Affiliations

¹ Chang-Kung Chuang Institute, School of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Lu, Shanghai 200241, China.
² Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, East China Normal University, 3663 North Zhongshan Lu, Shanghai 200062, China.

PMID: 33754741
DOI: 10.1021/acs.orglett.1c00498

Abstract

An unprecedented reductive [2 + 1] annulation of α-keto esters with alkynones mediated by P(NMe₂)₃ is described. Although this nonmetal cyclopropenation is a nucleophilic process, attributed to the ester migration via a formal [2 + 2] cycloaddition reaction of Kukhtin-Ramirez adducts and alkynones followed by a fragmentation, cyclopropenes with an unbiased alkene scaffold are formed in good to excellent yields, thus providing a promising complementarity to electrophilic metal-catalyzed cyclopropenation.