Journal
CHEMICAL SCIENCE
Volume 1, Issue 6, Pages 723-730Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0sc00276c
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Funding
- Lucite International
- University of St. Andrews
- EPSRC [EP/F019610/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/F019610/1] Funding Source: researchfish
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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 alpha,beta-unsaturated esters after short reaction times or alpha,omega-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.
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