Magic of alpha : the chemistry of a remarkable bidentate phosphine, 1,2-bis(di-tert-butylphosphinomethyl)benzene
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The bidentate phosphine ligand 1,2-bis(di-tert-butylphosphinomethyl)benzene (1,2-DTBPMB) has been reported over the years as being one of, if not the, best ligands for achieving the alkoxycarbonylation of various unsaturated compounds. Bonded to palladium, the ligand provides the basis for the first step in the commercial (Alpha) production of methyl methacrylate as well as very high selectivity to linear esters and acids from terminal or internal double bonds. The present review is an overview covering the literature dealing with the 1,2-DTBPMB ligand: from its first reference, its catalysis, including the alkoxycarbonylation reaction and its mechanism, its isomerization abilities including the highly selective isomerizing methoxycarbonylation, other reactions such as cross-coupling, recycling approaches, and the development of improved, modified ligands, in which some tert-butyl ligands are replaced by 2-pyridyl moieties and which show exceptional rates for carbonylation reactions at low temperatures.
Vondran , J , Furst , M R L , Eastham , G R , Seidensticker , T & Cole-Hamilton , D J 2021 , ' Magic of alpha : the chemistry of a remarkable bidentate phosphine, 1,2-bis(di- tert -butylphosphinomethyl)benzene ' , Chemical Reviews , vol. 121 , no. 11 , pp. 6610-6653 . https://doi.org/10.1021/acs.chemrev.0c01254
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DescriptionWe thank the Fonds der Chemischen Industrie for a Kekulé Fellowship for a studentship and the Deutsche Forschungsgemeinschaft (DFG, project number 424535516) for support (J.V.). We are also very grateful to Lucite International for funding the work in St Andrews that is contained in this review.
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