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Synthesis of multisubstituted 1,3-butadienes using the ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynylboronates
Ryotaro Morita,Eiji Shirakawa,Teruhisa Tsuchimoto,Yusuke Kawakami
Organic & Biomolecular Chemistry Pub Date : 02/28/2005 00:00:00 , DOI:10.1039/B501990G
Abstract

The ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynes developed by Dixneuf and co-workers was applied to the synthesis of 2-alkyl- or 2-aryl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,4-bis(trimethylsilyl)-1,3-butadienes by use of alkynylboronates instead of alkynes. Di- and tetrasubstituted 1,3-butadienes were prepared from a 2-boryl-1,4-disilyl-1,3-butadiene, using the Suzuki–Miyaura coupling reaction, iodolysis of the alkenylsilane moieties with N-iodosuccinimide and hydrolysis of the carbon–silicon bonds with trifluoroacetic acid. The same compound was converted also to a bicyclic compound, a trisubstituted 1,3-butadiene and a dienone through the Diels–Alder reaction, oxidation of the alkenylboronate moiety and the Mukaiyama aldol reaction.

Graphical abstract: Synthesis of multisubstituted 1,3-butadienes using the ruthenium-catalysed double addition of trimethylsilyldiazomethane to alkynylboronates
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