Carbene-catalyzed activation of remote nitrogen atoms of (Benz)imidazole-derived aldimines for enantioselective synthesis of heterocycles
A new mode of carbene-catalyzed heteroatom activation and asymmetric reactions is disclosed. The reaction starts with addition of a carbene catalyst to a (benz)imidazole-derived aldimine substrate. Subsequent oxidation and proton transfer lead to the formation of a catalyst-bound triaza-diene as the...
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Main Authors: | , , , , , , , , , , |
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Other Authors: | |
Format: | Article |
Language: | English |
Published: |
2021
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Subjects: | |
Online Access: | https://hdl.handle.net/10356/148222 |
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Institution: | Nanyang Technological University |
Language: | English |
Summary: | A new mode of carbene-catalyzed heteroatom activation and asymmetric reactions is disclosed. The reaction starts with addition of a carbene catalyst to a (benz)imidazole-derived aldimine substrate. Subsequent oxidation and proton transfer lead to the formation of a catalyst-bound triaza-diene as the key intermediate, in which the nitrogen atom at a site remote to the catalyst-substrate bond is activated. This unusual triaza-diene intermediate then undergoes highly enantioselective reactions with activated ketones through a concerted asynchronous pathway, as supported by mechanistic studies and preliminary density function theory calculation. |
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