Experimental and Computational Studies of Palladium-Catalyzed Spirocyclization via a Narasaka–Heck/C(sp3 or sp2)–H Activation Cascade Reaction

Autor:	Cui-Tian Wang, Ya-Ting Wen, Ming Li, Bo-Sheng Zhang, Rui-Qiang Jiao, Xue-Song Li, Yu Xia, Wan-Xu Wei, Yuke Li, Hong-Chao Liu, Yong-Min Liang
Rok vydání:	2021
Předmět:	In situ Tandem chemistry.chemical_element General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Catalysis 0104 chemical sciences Colloid and Surface Chemistry chemistry Cascade reaction Computational chemistry Density functional theory Palladium
Zdroj:	Journal of the American Chemical Society. 143:7868-7875
ISSN:	1520-5126 0002-7863
DOI:	10.1021/jacs.1c04114
Popis:	The first synthesis of highly strained spirocyclobutane-pyrrolines via a palladium-catalyzed tandem Narasaka-Heck/C(sp3 or sp2)-H activation reaction is reported here. The key step in this transformation is the activation of a δ-C-H bond via an in situ generated σ-alkyl-Pd(II) species to form a five-membered spiro-palladacycle intermediate. The concerted metalation-deprotonation (CMD) process, rate-determining step, and energy barrier of the entire reaction were explored by density functional theory (DFT) calculations. Moreover, a series of control experiments was conducted to probe the rate-determining step and reversibility of the C(sp3)-H activation step.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::6b5105cb7e9f8c0a923dc43ac301d3df https://doi.org/10.1021/jacs.1c04114 Zobrazit plný text záznamu