Authors: Naapuri, JM; Aberg, GA; Palomo, JM; Deska, J

Article; Early Access.
ChemCatChem. vol: . page: 1867-3880.
Date: . 03 December 2020
Doi: 10.1002/cctc.202001619.

The one-pot combination of halogenation biocatalysis and Suzuki-type cross coupling enables the direct arylative cyclization of allenic alcohols with boronic acids. This modular approach to unsaturated five-membered O-heterocycles proceeds in an aqueous emulsion with air as terminal oxidant. Here, the enzymatic oxidative activation of simple halide salts acts as traceless ring-closure-inducing event to trigger the subsequent C-C coupling. With the original protocol merging soluble proteins and a homogeneous SPhos-based palladium catalyst as a template, a novel heterogeneous nanobiohybrid was developed. Consisting of an oxidase matrix hosting small spherical palladium nanoparticles, this enzyme-metal hybrid exhibits catalytic competence for both the biocyclization as well as the C-C bond-forming cross coupling, underlining the potential of this new techniques for streamlining chemoenzymatic approaches..