Reaction of Alkynyl- And Alkenyltrifluoroborates with Propargyldicobalt Cations: Alkynylation, Alkenylation, and Cyclopropanation Product Pathways

Authors

Brent St Onge, University of Windsor
S. Maryamdokht Taimoory, University of Windsor
Jeffrey Battersby, University of Windsor
John F. Trant, University of Windsor
James R. Green, University of Windsor

Document Type

Article

Publication Date

12-17-2021

Publication Title

Journal of Organic Chemistry

Volume

86

Issue

24

First Page

18094

Last Page

18106

Abstract

The Lewis acid-mediated Nicholas reactions of propargyl acetate–Co2(CO)6 complexes with a series of potassium alkynyltrifluoroborates and potassium alkenyltrifluoroborates are described. Alkynyltrifluoroborates directly alkynylate the intermediate propargyldicobalt cations. In contrast, alkenyltrifluoroborates proceed through one of the three modes of dominant reactivity: C-2-substituted alkenyltrifluorobrates directly alkenylate, predominantly with the retention of stereochemistry. C-1-substituted alkenyltrifluoroborates alkenylate at C-2. Potassium vinyltrifluoroborate incorporates a cyclopropane at the site propargyl to alkynedicobalt. Computational analysis of these systems explains the differential modes of reactivity of alkenyltrifluoroborates and outlines the probable mechanisms for the formation of each product.

DOI

10.1021/acs.joc.1c02352

ISSN

00223263

E-ISSN

15206904

Recommended Citation

St Onge, Brent; Taimoory, S. Maryamdokht; Battersby, Jeffrey; Trant, John F.; and Green, James R.. (2021). Reaction of Alkynyl- And Alkenyltrifluoroborates with Propargyldicobalt Cations: Alkynylation, Alkenylation, and Cyclopropanation Product Pathways. Journal of Organic Chemistry, 86 (24), 18094-18106.
https://scholar.uwindsor.ca/chemistrybiochemistrypub/169