铑催化的苯并环丁烯酮与苯乙烯型烯烃之间的(4+1)环加成反应
Rhodium-Catalyzed (4+1) Cycloaddition between Benzocyclobutenones and Styrene-Type Alkenes.
作者信息
Ochi Shusuke, Zhang Zining, Xia Ying, Dong Guangbin
机构信息
Department of Chemistry, The University of Chicago, 5735 S Ellis Ave, Chicago, IL 60637, USA.
出版信息
Angew Chem Int Ed Engl. 2022 May 23;61(22):e202202703. doi: 10.1002/anie.202202703. Epub 2022 Mar 30.
Abstract
Herein, we describe a unique one-carbon ring-expansion strategy to access multi-substituted 2-indanones from benzocyclobutenones and styrene-type olefins. The use of a cationic "ligandless" rhodium catalyst was the key for both high reactivity and selectivity towards the (4+1) product. Broad functional group tolerance, a good substrate scope, and scalability have been demonstrated. Computation studies reveal that the origin of the (4+1) selectivity is due to a facile β-H elimination pathway that reduces the overall barrier of the turnover-limiting C-C reductive elimination step.
摘要
在此，我们描述了一种独特的单碳环扩展策略，可从苯并环丁烯酮和苯乙烯型烯烃合成多取代的2-茚酮。使用阳离子“无配体”铑催化剂是实现对（4+1）产物具有高反应活性和选择性的关键。该反应展现出广泛的官能团耐受性、良好的底物范围和可扩展性。计算研究表明，（4+1）选择性的起源是由于一条容易发生的β-H消除途径，该途径降低了周转限制的C-C还原消除步骤的整体势垒。
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