posted on 2024-02-01, 16:09authored byXiaoming Xu, Ailin Gao, Xiufang Xu, Jianfeng Li, Chunming Cui
Methylenecyclopropanes
(MCPs) have emerged as versatile building
blocks in synthetic chemistry because of their unique reactivity.
However, metal-catalyzed hydrosilylation of MCPs has met with very
limited successes. In this paper, catalytic selective hydrosilylations
of MCPs with some primary silanes using an ene-diamido lanthanum ate
complex as the catalyst were described. The catalytic reactions resulted
in the selective formation of silacyclopentanes and (E)-homoallylsilanes, respectively, depending on the substituents on
MCPs. The formation of silacyclopentanes via a catalytic cascade inter-
and intramolecular hydrosilylation mechanism is strongly supported
by the control and deuteration-labeling experiments and DFT calculations.
The unique reactivity and selectivity could be attributed to the large
lanthanum ion and ate structure of the catalyst.