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Chelated Diborenes and Their Inverse-Electron-Demand Diels-Alder Reactions with Dienes
Tom E Stennett1,2, James D Mattock3, Leanne Pentecost3
1Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg, Am Hubland, 97070, Würzburg, Germany.
Abstract:
A doubly base-stabilised diborane based on a benzylphosphine linker was prepared by a salt elimination reaction between 2-LiC6 H4 CH2 PCy2 ⋅Et2 O and B2 Br4 . 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.
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