[4 + 1]- and [4 + 2]-cycloadditions of a thiazole-2-thione-based 1,4-diphosphinine - broadening the scope

Tim Kalisch; Gregor Schnakenburg; Georgii I Nikonov; Rainer Streubel

doi:10.1039/d4dt02029d

[4 + 1]- and [4 + 2]-cycloadditions of a thiazole-2-thione-based 1,4-diphosphinine - broadening the scope

Dalton Trans. 2024 Oct 1;53(38):16018-16022. doi: 10.1039/d4dt02029d.

Authors

Tim Kalisch¹, Gregor Schnakenburg¹, Georgii I Nikonov², Rainer Streubel¹

Affiliations

¹ Institute of Inorganic Chemistry, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53123 Bonn, Germany. [email protected].
² Department of Chemistry, Brock University, 1812 Sir Isaac Brock Way, St Catharines, ON, L2S 3A1, Canada. [email protected].

PMID: 39290091
DOI: 10.1039/d4dt02029d

Abstract

A broad study on [4 + 1]- and [4 + 2]-cycloaddition reactions of a thiazole-2-thione-based 1,4-diphosphinine (1) is reported, with a special focus on reversible reactions. Reactions of 1 with group 13 carbenoids ^DippNacNacM (M = Al and Ga) afford [4 + 1] adducts that can be classified as Al and Ga phosphides or as 7-metalla-1,4-norbornadienes. Reactions of 1 with alkynes and alkenes result in [4 + 2]-cycloaddition, affording 1,4-diphosphabarrelenes. The effect of different dienophiles on the formation of 1,4-diphosphabarrelenes and their thermal [4 + 2]-cycloreversion reactions is studied from an experimental as well as theoretical point of view, opening the door for protection/deprotection strategies in this chemistry.