Catalytic 4-exo-dig carbocyclization for the construction of furan-fused cyclobutanones and synthetic applications.
Catalytic 4-exo-dig carbocyclization for the construction of furan-fused cyclobutanones and synthetic applications.
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DOI：
10.1038/s41467-023-42032-9
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发表时间：
2023-10-11
影响因子：
16.6
通讯作者：
Xu, Xinfang
中科院分区：
文献类型：
--
作者：
Hong, Kemiao;Zhou, Yi;Yuan, Haoxuan;Zhang, Zhijing;Huang, Jingjing;Dong, Shanliang;Hu, Wenhao;Yu, Zhi-Xiang;Xu, Xinfang
Cyclobutanone is a strained motif with broad applications, while direct assembly of the aromatic ring fused cyclobutanones beyond benzocyclobutenone (BCB) skeletons remains challenging. Herein, we report a Rh-catalyzed formal [3+2] annulation of diazo group tethered alkynes involving a 4-exo-dig carbocyclization process, providing a straightforward access to furan-fused cyclobutanones. DFT calculations disclose that, by comparison to the competitive 5-endo-dig process, 4-exo-dig carbocyclization is mainly due to lower angle strain of the key sp-hybridized vinyl cationic transition state in the cyclization step. Using less reactive catalysts Rh2(carboxylate)4 is critical for high selectivity, which is explained as catalyst-substrate hydrogen bonding interaction. This method is proved successful to direct access previously inaccessible and unknown furan-fused cyclobutanone scaffolds, which can participate in a variety of post-functionalization reactions as versatile synthetic blocks. In addition, preliminary antitumor activity study of these products indicates that some molecules exhibite significant anticancer potency against different human cancer cell lines. Aromatic ring fused cyclobutanone is a strained motif with broad applications. Here, the authors report a catalytic 4- exo-dig process, which proved successful to access furan-fused cyclobutanones that can serve as versatile synthetic blocks.
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影响因子：
16.6
作者：
Diaz-Jimenez, Alex;Monreal-Corona, Roger;Poater, Albert;Alvarez, Maria;Borrego, Elena;Perez, Pedro J.;Caballero, Ana;Roglans, Anna;Pla-Quintana, Anna
通讯作者：
Pla-Quintana, Anna
影响因子：
4.9
作者：
Alcaide, Benito;Almendros, Pedro;Fernandez, Israel
通讯作者：
Fernandez, Israel
具有应变环丙烷和/或环丁烷环系统的有吸引力的天然产物
影响因子：
9.6
作者：
Fan, Yao-Yue;Gao, Xin-Hua;Yue, Jian-Min
通讯作者：
Yue, Jian-Min
影响因子：
15
作者：
HAMMOND, GS
通讯作者：
HAMMOND, GS
影响因子：
3.6
作者：
BRADLEY, JC;DURST, T;WILLIAMS, AJ
通讯作者：
WILLIAMS, AJ