%0 Journal Article %T Phosphinocyclodextrins as confining units for catalytic metal centres. Applications to carbon-carbon bond forming reactions %+ Institut de Chimie de Strasbourg %+ Istituto di Chimica dei Composti Organometallici (ICCOM) %+ Groupe matière condensée et matériaux (GMCM) %A Jouffroy, Matthieu %A Gramage-Doria, Rafael %A Sémeril, David %A Armspach, Dominique %A Matt, Dominique %A Oberhauser, Werner %A Toupet, Loic %< avec comité de lecture %@ 1860-5397 %J Beilstein Journal of Organic Chemistry %I Beilstein-Institut %V 10 %P 2388-2405 %8 2014 %D 2014 %R 10.3762/bjoc.10.249 %K asymmetric hydroformylation %K cyclodextrin %K Heck reaction %K homogeneous catalysis %K palladium %K phosphine %K rhodium %Z Chemical Sciences/Organic chemistry %Z Chemical Sciences/CatalysisJournal articles %X 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. %G English %2 https://univ-rennes.hal.science/hal-01472884/document %2 https://univ-rennes.hal.science/hal-01472884/file/1860-5397-10-249.pdf %L hal-01472884 %U https://univ-rennes.hal.science/hal-01472884 %~ UNIV-RENNES1 %~ CNRS %~ UNIV-STRASBG %~ OSUR %~ IPR %~ ZZ-IPR-MN %~ UR1-SPM %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ UR1-SDLM %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ SITE-ALSACE %~ UNIV-RENNES %~ UR1-MMS %~ TEST2-HALCNRS