%0 Journal Article %T [3,3]-Sigmatropic Rearrangement/Allylboration/Cyclization Sequence: Enantioenriched Seven-Membered-Ring Carbamates and Ring Contraction to Pyrrolidines %+ Institut des Sciences Chimiques de Rennes (ISCR) %A Macé, Aurélie %A Touchet, Sabrina %A Andres, Patricia %A Cossío, Fernando %A Dorcet, Vincent %A Carreaux, François %A Carboni, Bertrand %< avec comité de lecture %@ 0044-8249 %J Angewandte Chemie %I Wiley-VCH Verlag %V 55 %N 3 %P 1025–1029 %8 2016 %D 2016 %R 10.1002/anie.201509824 %M 26636973 %K allylic compounds %K asymmetric synthesis %K Heterocycles %K reaction mechanisms %K rearrangements %Z Chemical SciencesJournal articles %X The combination of in situ generated α-isocyanato allylboronic esters and aldehydes afforded seven-membered-ring enecarbamates with high levels of diastereo- and enantiocontrol. They were easily converted into diversely substituted 1,3-oxazepan-2-ones. An unprecedented rearrangement of 5-acetoxy-7-aryl or styryl derivatives led to tetrasubstituted pyrrolidines. A computational study provides evidence on the feasibility of the proposed mechanism of this unusual ring contraction %G English %L hal-01240655 %U https://univ-rennes.hal.science/hal-01240655 %~ UNIV-RENNES1 %~ CNRS %~ INSA-RENNES %~ ENSC-RENNES %~ ISCR %~ SCR_ICMV %~ STATS-UR1 %~ UR1-SPM %~ ISCR-PRATS %~ INC-CNRS %~ UR1-UFR-SPM %~ UR1-HAL %~ ISCR-CORINT %~ UR1-SDLM %~ TEST-UNIV-RENNES %~ TEST-UR-CSS %~ UNIV-RENNES %~ INSA-GROUPE %~ ISCR-CORINT1 %~ UR1-MMS %~ TEST2-HALCNRS