Nickel-catalyzed acylzincation of allenes with organozincs and CO

Xianqing Wu; Chenglong Wang; Ning Liu; Jingping Qu; Yifeng Chen

doi:10.1038/s41467-023-42716-2

Nickel-catalyzed acylzincation of allenes with organozincs and CO

Nat Commun. 2023 Oct 31;14(1):6960. doi: 10.1038/s41467-023-42716-2.

Authors

Xianqing Wu¹, Chenglong Wang¹, Ning Liu¹, Jingping Qu¹, Yifeng Chen²

Affiliations

¹ Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology 130 Meilong Road, Shanghai, China.
² Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology 130 Meilong Road, Shanghai, China. yifengchen@ecust.edu.cn.

Abstract

Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling the construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence of allene and alkylzinc reagent with 1 atm of CO under mild conditions. This protocol is featured by broad functional group tolerance with high reaction selectivity, providing a rapid and convenient synthetic method for the construction of diverse fully substituted benzotropone derivatives. Mechanistic studies reveal that the installation of a cyano group tethered to allene moiety enables the high regio- and stereoselectivity of this acylzincation of allene, allowing the selective formation of three consecutive C-C bonds in a highly efficient manner.