Copper and Nickel Promoted Transformations of Alkyne based Cyclic Carbonates

Identifier:  TDX:3674

Handle: https://hdl.handle.net/20.500.11797/TDX3674

Authors:  Guo, Kun

Abstract:
The development of TM-catalyzed propargylic substitution or SN2'-type reactions of propargylic cyclic carbonates and related heterocycles has provided an efficient strategy to construct complex organic molecules and materials. Even though Cu catalysis has been shown to be very successful in promoting the asymmetric propargylic substitution of terminal alkyne-substituted cyclic carbonates via Cu−allenylidene intermediates, Cu-catalyzed SN2'-type reactions of internal alkyne-substituted cyclic carbonates or similar heterocycles remains unexplored. Based on previous reports and recent achievements in our group, we envisioned that the development of Cu-promoted decarboxylative functionalization of (internal) alkyne-substituted cyclic carbonates with silylboron or diboron(4) reagents would potentially provide new reactivity paradigms while giving additional insights into the operating mode of the catalyst and delivering a more ample range of synthetically useful compounds. In addition, new catalytic protocols that can foster the easy preparation of enantioenriched products via stereospecific Ni-catalyzed reactions would also be an attractive target. Considering that organosilicon and organoboron compounds are characterized by stability, nontoxicity, and easy handling, the development of these compounds is believed to contribute to amplify the synthetic toolbox of organic chemists offering new synthetic opportunities for a wide range of fine-chemical targets.