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Published on: November 9, 2019
Stereocontrolled Synthesis of α-Branched Tetrahydropyrans by a One-Pot-Two-Step Photobiocatalytic Cascade of
Claudio Zippilli1, Elisa De Marchi1, Beatrice Di Maio1
1Department of Biological and Ecological Sciences, University of Tuscia, Via S.C. De Lellis, s.n.c., 01100 Viterbo, Italy.
Abstract:
The monoterpene citronellol often represents the substrate for the synthesis of other natural products and fragrances bearing α-branched tetrahydropyran moieties. In this contribution, we developed a process that combines in one-pot condition photocatalytic Schenck-ene reaction and biocatalytic halocyclization to synthesize enantiopure α-branched tetrahydropyrans starting from natural monoterpene citronellol. The reaction pathway of the enzymatic haloetherification, studied by combining experimental and theoretical studies, showed for the first time the key role played by the hydroperoxide functional group in the control of the regioselectivity of the cyclization step. Overall, a novel and sustainable synthetic procedure is reported as a new approach for α-branched tetrahydropyrans.
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