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Preparation and Use of Carbonyl-decorated Carbenes in the Activation of White Phosphorus
Published on: October 3, 2014
Electrochemically driven regioselective C-H phosphorylation of group 8 metallocenes
Hao Zheng1,2, Chang-Hui Liu1,2, Shi-Yu Guo1
1Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian, 116023, China.
Abstract:
Metallocenes are privileged backbones for synthesis and catalysis. However, the direct dehydrogenative C-H functionalization of unsymmetric metallocenes suffers from reactivity and selectivity issues. Herein, we report an electrochemically driven regioselective C-H phosphorylation of group 8 metallocenes. Mechanistic investigations indicate this dehydrogenative cross coupling occurs through an electrophilic radical substitution of the metallocene with a phosphoryl radical, facilitated by the metallocene itself. This work not only offers an efficient and divergent synthesis of phosphorylated metallocenes, but also provides a guide to interpret the reactivity and regioselectivity for the C-H functionalization of unsymmetric metallocenes.
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