|
|||||
|
|
Catalytic Asymmetric Syntheses of Alkylidenecyclopropanes from Allenoates with Donor-Acceptor and Diacceptor Diazo Reagents |
|
| Authors: | Dr Yoko Hasegawa Dr Thomas Cantin Dr Jonathan Decaens Dr Samuel Couve-Bonnaire Prof Dr André B Charette Prof Dr Thomas Poisson Prof Dr Philippe Jubault |
| Institution: | 1. Normandie Univ., INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France
These authors contributed equally to this work.;2. Normandie Univ., INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France;3. Université de Montréal, FRQ-NT Centre in Green Chemistry and Catalysis, Department of Chemistry, 1375, av. Thérèse Lavoie-Roux, Montréal, QC H2 V 0B3 Canada;4. Normandie Univ., INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000 Rouen, France Institut Universitaire de France, 1 rue Descartes, 75231 Paris, France |
| Abstract: | The first diastereo- and enantioselective cyclopropanation reactions of electron-deficient allenes with donor-acceptor and diacceptor diazo reagents are described. The desired enantioenriched alkylidenecyclopropanes (ACPs) were obtained in high yields with high diastereo- and enantioselectivities in the presence of Rh2((S)-TCPTAD)4 or Rh2((R)-BTPCP)4 catalysts (up to 95 % yield, >95 : 5 d.r. and 99 : 1 e.r.). This methodology gave a direct access to ACPs bearing multiple electron-deficient substituents and allows to further expand the availability of ACPs chemistry. Interestingly, during the examination of the scope of this reaction, the asymmetric intramolecular C−H insertion reaction into tert-butyl group was observed as a side reaction with up to 94 : 6 e.r. |
| Keywords: | alkylidene cyclopropanes allenoates diazo reagent asymmetric synthesis rhodium catalyst |