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Synfacts 2020; 16(10): 1171
DOI: 10.1055/s-0040-1706446
DOI: 10.1055/s-0040-1706446
Metals in Synthesis
Rhodium-Catalyzed Enantioselective Diarylcarbene Insertion into Si–H Bonds
Yang L.-L,
Evans D,
Xu B,
Li W.-T,
Li M.-L,
Zhu S.-F,
*,
Houk KN,
*,
Zhou Q.-L.
*
Nankai University, Tianjin, P. R. of China and University of California, Los Angeles, USA
Enantioselective Diarylcarbene Insertion into Si–H Bonds Induced by Electronic Properties of the Carbenes.
J. Am. Chem. Soc. 2020;
142: 12394-12399
Enantioselective Diarylcarbene Insertion into Si–H Bonds Induced by Electronic Properties of the Carbenes.
J. Am. Chem. Soc. 2020;
142: 12394-12399
Significance
The authors describe a rhodium-catalyzed asymmetric coupling of silanes with diaryldiazomethanes. The enantioselection is shown to be induced by the electronic properties of the aryl substituents of the carbene rather than sterics.
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Comment
DFT studies support the conclusion that, in the favored transition state, the more electron-rich aryl group is coplanar with the carbene empty p-orbital while the other ring is orthogonal, resulting in their differentiation.
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Publication History
Article published online:
17 September 2020
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