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Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon-carbon bond forming reactions

Abstract : The capacity of two cavity-shaped ligands, HUGPHOS-1 and HUGPHOS-2, to generate exclusively singly phosphorus-ligated complexes, in which the cyclodextrin cavity tightly wraps around the metal centre, was explored with a number of late transition metal cations. Both cyclodextrin-derived ligands were assessed in palladium-catalysed Mizoroki–Heck coupling reactions between aryl bromides and styrene on one hand, and the rhodium-catalysed asymmetric hydroformylation of styrene on the other hand. The inability of both chiral ligands to form standard bis(phosphine) complexes under catalytic conditions was established by high-pressure NMR studies and shown to have a deep impact on the two carbon–carbon bond forming reactions both in terms of activity and selectivity. For example, when used as ligands in the rhodium-catalysed hydroformylation of styrene, they lead to both high isoselectivity and high enantioselectivity. In the study dealing with the Mizoroki–Heck reactions, comparative tests were carried out with WIDEPHOS, a diphosphine analogue of HUGPHOS-2.
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Matthieu Jouffroy, Rafael Gramage-Doria, David Sémeril, Dominique Armspach, Dominique Matt, et al.. Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon-carbon bond forming reactions. Beilstein Journal of Organic Chemistry, Beilstein-Institut, 2014, 10, pp.2388-2405. ⟨10.3762/bjoc.10.249⟩. ⟨hal-01472884⟩

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