Ni-catalyzed asymmetric hydrophosphinylation of conjugated enynes and mechanistic studies

Chem Sci. 2022 Mar 10;13(14):4095-4102. doi: 10.1039/d2sc00091a. eCollection 2022 Apr 6.

ABSTRACT

The catalytic asymmetric synthesis of P-stereogenic phosphines is an efficient strategy to access structurally diverse chiral phosphines that could serve as organocatalysts and ligands to transition metals and motifs of antiviral drugs. Herein, we describe a Ni catalyzed highly regio and enantioselective hydrophosphinylation reaction of secondary phosphine oxides and enynes. This method afforded a plethora of alkenyl phosphine oxides which could serve as valuable precursors to bidentate ligands. A new type of mechanism was discovered by combined kinetic studies and density functional theory (DFT) calculations, which was opposed to the widely accepted Chalk-Harrod type mechanism. Notably, the alkene moiety which could serve as a directing group by coordinating with the Ni catalyst in the transition state, plays a vital role in determining the reactivity, regio and enantioselectivity.

PMID:35440997 | PMC:PMC8985578 | DOI:10.1039/d2sc00091a

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