Enantioselective Si–H Insertion Reactions of Diarylcarbenes for the Synthesis of Silicon-Stereogenic Silanes

• Published in: Journal of the American Chemical Society Vol. 142; no. 27; pp. 11674 - 11679
• Main Authors: Jagannathan, Jake R, Fettinger, James C, Shaw, Jared T, Franz, Annaliese K
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 08-07-2020
• Subjects: Catalysis; Hydrogen - chemistry; Methane - analogs & derivatives; Methane - chemistry; Molecular Structure; Organometallic Compounds - chemistry; Silanes - chemical synthesis; Silanes - chemistry; Silicon - chemistry; Stereoisomerism
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/jacs.0c04533

We report the first example of enantioselective, intermolecular diarylcarbene insertion into Si–H bonds for the synthesis of silicon-stereogenic silanes. Dirhodium­(II) carboxylates catalyze an Si–H insertion using carbenes derived from diazo compounds where selective formation of an enantioenriched silicon center is achieved using prochiral silanes. Fourteen prochiral silanes were evaluated with symmetrical and prochiral diazo reactants to produce a total of 25 novel silanes. Adding an ortho substituent on one phenyl ring of a prochiral diazo enhances enantioselectivity up to 95:5 er with yields up to 98%. Using in situ IR spectroscopy, the impact of the off-cycle azine formation is supported based on the structural dependence for relative rates of diazo decomposition. A catalytic cycle is proposed with Si–H insertion as the rate-determining step, supported by kinetic isotope experiments. Transformations of an enantioenriched silane derived from this method, including selective synthesis of a novel sila-indane, are demonstrated.