Citation: Zhihua Wang, Li Wei, Zhendong Cheng, Jianhui Xia, Zhiyuan Chen. Pd-catalyzed halocyclizations of unactivated 1, 6-diynes through a formal anti-carbopalladation/bromide radical cascade[J]. Chinese Chemical Letters, ;2021, 32(9): 2756-2760. doi: 10.1016/j.cclet.2021.03.030 shu

Pd-catalyzed halocyclizations of unactivated 1, 6-diynes through a formal anti-carbopalladation/bromide radical cascade

Key Laboratory of Functional Small Organic Molecules, Ministry of Education and Jiangxi Key Laboratory of Green Chemistry, College of Chemistry & Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China

xjh2168@126.com

zchen@jxnu.edu.cn

27542458@qq.com

Received Date: 21 January 2021
Revised Date: 3 March 2021
Accepted Date: 12 March 2021
Available Online: 15 March 2021

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We report a Pd-catalyzed halocyclization of unactivated 1, 6-diynes with N-bromosuccinimide (NBS). This approach produces stereo-defined dibromo substituted dihydropyrans, tetrahydropyridines, and 3-methylene cyclohexenes with exocyclic double bond appendages in mostly good yields. Copper salt was found to be a useful Lewis acid in this reaction. Mechanistically, a formal anti-carbopalladation and a bromide radical promoted Pd^II-Pd^III-Pd^I-Pd^II catalytic cycles were proposed to be involved in the formation of the dibromo-substituted products. Further functionalization of the dihydropyran derivatives underwent B(C₆F₅)₃-catalyzed ring opening, and reduction afforded dibrominated 1, 3-dienes with excellent stereoselectivity.
- Palladium catalysis,
- Halocyclization,
- Unactivated diyne,
- anti-Carbopalladation,
- Bromide radical,
- 1, 3-Diene
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