Nickel-catalyzed divergent Mizoroki-Heck reaction of 1,3-dienes.

Zhang, Wei-Song; Ji, Ding-Wei; Li, Ying; Zhang, Xiang-Xin; Mei, Yong-Kang; Chen, Bing-Zhi; Chen, Qing-An · Nat Commun · 2023

basic_science · Level V

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Abstract

Developing efficient strategies to realize divergent arylation of dienes has been a long-standing synthetic challenge. Herein, a nickel catalyzed divergent Mizoroki-Heck reaction of 1,3-dienes has been demonstrated through the regulation of ligands and additives. In the presence of Mn/NEt<sub>3</sub>, the Mizoroki-Heck reaction of dienes delivers linear products under Ni(dppe)Cl<sub>2</sub> catalysis in high regio- and stereoselectivities. With the help of catalytic amount of organoboron and NaF, the use of bulky ligand IPr diverts the selectivity from linear products to branched products. Highly aryl-substituted compounds can be transformed from dispersive Mizoroki-Heck products programmatically. Preliminary experimental studies are carried out to elucidate the role of additives.