Cyclopropenylcarbinol derivatives as new versatile intermediates in organic synthesis: application to the formation of enantiomerically pure alkylidenecyclopropane derivatives.
The copper-catalyzed carbomagnesiation (or hydrometalation) reaction of chiral cyclopropenylcarbinol derivatives, obtained by means of a kinetic resolution of secondary allylic alcohols, leads to an easy and straightforward preparation of enantiomerically pure alkylidenecyclopropane derivatives. The reaction mechanism is composed of a syn-carbometalation followed by a syn-elimination reaction. To gain further insight into the reaction mechanism of the carbometalation, the diastereoselective formation of cyclopropylcarbinol was also achieved and was found to be very sensitive to the nature of the organometallic species used for the addition reaction. Cyclopropylcarbinol could also be prepared through a diastereoselective reduction of cyclopropenylcarbinol derivatives. Finally, functionalization of enantiomerically enriched cyclopropenylcarbinols into the corresponding acetate or phosphinite derivatives leads, under mild conditions, to various enantiomerically pure heterosubstituted alkylidenecyclopropanes.
Simaan
Samah
S
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry, and the Lise Meitner-Minerva, Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000 (Israel), Fax: (+972) 4 829 3709.
Masarwa
Ahmad
A
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry, and the Lise Meitner-Minerva, Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000 (Israel), Fax: (+972) 4 829 3709.
Zohar
Elinor
E
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry, and the Lise Meitner-Minerva, Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000 (Israel), Fax: (+972) 4 829 3709.
Stanger
Amnon
A
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry, and the Lise Meitner-Minerva, Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000 (Israel), Fax: (+972) 4 829 3709.
Bertus
Philippe
P
CNRS UMR 6011, Unite de Chimie Organique et Moleculaire (UCO2M), Universite du Maine, Avenue O. Messian, 72085 Le Mans Cedex 9 (France).
Marek
Ilan
I
The Mallat Family Laboratory of Organic Chemistry, Schulich Faculty of Chemistry, and the Lise Meitner-Minerva, Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000 (Israel), Fax: (+972) 4 829 3709.