Chelated diborenes and their inverse-electron-demand Diels-Alder reactions with dienes

Stennett, Tom, Mattock, James D, Pentecost, Leanne, Vargas, Alfredo and Braunschweig, Holger (2018) Chelated diborenes and their inverse-electron-demand Diels-Alder reactions with dienes. Angewandte Chemie International Edition, 57 (46). pp. 15276-15281. ISSN 1521-3773

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Abstract

A doubly base-stabilized diborane based on a benzylphosphine linker was prepared by a salt elimination reaction between 2-LiC6H4CH2PCy2.Et2O and B2Br4. This compound was reduced with KC8 to its corresponding diborene, with the benzylphosphine forming a five-membered chelate. The diborene reacts with butadiene, 2-trimethylsiloxy-1,3-butadiene and isoprene to form 4,5-diboracyclohexenes, which interconvert between their 1,1- (geminal) and 1,2- (vicinal) chelated isomers. The 1,1-chelated diborene undergoes a halide-catalysed isomerisation into its thermodynamically favoured 1,2-isomer, which undergoes Diels-Alder reactions more slowly than the kinetic product.

Item Type: Article
Schools and Departments: School of Life Sciences > Chemistry
Subjects: Q Science > QD Chemistry
Depositing User: Alfredo Vargas
Date Deposited: 20 Sep 2018 13:53
Last Modified: 06 Dec 2018 14:23
URI: http://sro.sussex.ac.uk/id/eprint/78884

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