Shi-Hao Chen, Shengye Zhang, Zi-Yang Chen, Yichen Wu, Peng Wang
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Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket
Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge–H and Si–H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for the preparation of enantioenriched α-trifluoromethyl ogranogermanes and organosilanes, featuring a broad substrate scope, mild reaction conditions, excellent enantioselectivity, and low catalyst loading. The key to the tolerance of both Si–H and Ge–H bonds is the use of SPSiBox ligands bearing a flexible and tunable chiral pocket. Preliminary mechanistic studies and computational studies unveiled the origin of chiral induction with SPSiBox ligands, the mechanism of Cu-catalyzed Ge–H insertion. This method not only provides a new method for the construction of trifluoromethyl-containing chiral molecules but also opens a new avenue for the preparation of chiral Si- and Ge-containing functional molecules.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.