Highly selective formation of unsaturated esters or cascade reactions to α,ω-diesters by the methoxycarbonylation of alkynes catalysed by palladium complexes of 1,2-bis(ditertbutylphosphinomethyl)benzene?

Chemical Science Pub Date: 2010-10-14 DOI: 10.1039/C0SC00276C

Abstract

The methoxycarbonylation of phenylethyne catalysed by Pd/1,2-bis-(ditertiarybutylphosphinomethyl)benzene gives the unusual linear product, methyl cinnamate with high activity (initial turnover frequency, TOFo > 1700 mol product·(mol catalyst·h)?1) and regioselectivity (>90%). Terminal aliphatic alkynes give α,β–unsaturated esters after short reaction times or α,ω-diesters, including dimethyl 1,6-hexanedioate (dimethyl adipate), from 1-butyne after longer times. The diesters are formed by a cascade methoxycarbonylation–isomerisation–methoxycarbonylation sequence. Methoxycarbonylation of internal alkynes (e.g. 4-octyne) leads to the formation of the mono-carbonylated product as a result of the low propensity of the tri-substituted double bond of the product towards isomerisation. Hydroxycarbonylation of phenylethyne gives predominantly E-3-phenylpropanoic acid with smaller amounts of branched and disubstituted products as well as 3-phenylpropanoic acid. Evidence is presented that the reactions occur via a hydride mechanism.

Graphical abstract: Highly selective formation of unsaturated esters or cascade reactions to α,ω-diesters by the methoxycarbonylation of alkynes catalysed by palladium complexes of 1,2-bis(ditertbutylphosphinomethyl)benzene
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