Issue 23, 2024

Vinylidene rearrangements of internal borylalkynes via 1,2-boryl migration

Abstract

Vinylidene rearrangement of alkynes is a well-established and powerful method for alkyne transformations, while use of borylalkynes has remained largely unexplored. This paper describes vinylidene rearrangements of internal borylalkynes using a cationic ruthenium complex. This rearrangement is applicable to alkynes with both tri-(B(pin), B(dan)) and tetracoordinate (B(mida)) boryl groups, and the reaction rate is dramatically affected by the Lewis acidity of the boryl group. Mechanistic study revealed that the rearrangement proceeds via 1,2-boryl migration regardless of the coordination number of the boron center. The migration mode was elucidated by theoretical calculations to indicate that the migration of the tricoordinate boryl groups is an electrophilic process in contrast to the previous vinylidene rearrangements of internal alkynes with two carbon substituents.

Graphical abstract: Vinylidene rearrangements of internal borylalkynes via 1,2-boryl migration

Supplementary files

Article information

Article type
Paper
Submitted
09 abr. 2024
Accepted
21 may. 2024
First published
28 may. 2024

Dalton Trans., 2024,53, 9715-9723

Vinylidene rearrangements of internal borylalkynes via 1,2-boryl migration

T. Iwamoto, T. Mitsubo, K. Sakajiri and Y. Ishii, Dalton Trans., 2024, 53, 9715 DOI: 10.1039/D4DT01042F

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