TY - JOUR

T1 - Mn aminopyridine oxidase mimics

T2 - Switching between biosynthetic-like and xenobiotic regioselectivity in C–H oxidation of (-)-ambroxide

AU - Ottenbacher, Roman V.

AU - Samsonenko, Denis G.

AU - Nefedov, Andrey A.

AU - Talsi, Evgenii P.

AU - Bryliakov, Konstantin P.

N1 - Funding Information: This work was supported by the Russian Science Foundation (#20-13-00032). RVO, EPT and KPB gratefully acknowledge the access to the facilities of the shared research center ?National center of investigation of catalysts?, kindly provided by Boreskov Institute of Catalysis. The authors are grateful to the Collective Chemical Service Center of Siberian Branch of Russian Academy of Sciences for the HRMS measurements. Funding Information: This work was supported by the Russian Science Foundation (# 20-13-00032 ). RVO, EPT and KPB gratefully acknowledge the access to the facilities of the shared research center “National center of investigation of catalysts”, kindly provided by Boreskov Institute of Catalysis. The authors are grateful to the Collective Chemical Service Center of Siberian Branch of Russian Academy of Sciences for the HRMS measurements. Publisher Copyright: © 2021 Elsevier Inc. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/7

Y1 - 2021/7

N2 - The late-stage C–H oxofunctionalization of (-)-ambroxide with H2O2 in the presence of bioinspired honheme Mn complexes is reported. Adjusting the ligand architecture and absolute chirality, as well as tuning the reaction solvent, allows switching the catalysts’ selectivity between biosynthetic-like and bioorthogonal modes, thus directing the reaction towards either (+)-sclareolide or 2α-hydroxyambroxide, respectively. This opens the ways to 2,12-dihydroxyambroxide, 2α-hydroxysclareolide, ambroxide-2-one, ambroxide-2,12-dione, and several other, including previously unavailable, oxidized metabolites of (-)-ambroxide in synthetically meaningful yields, using the same catalyst systems.

AB - The late-stage C–H oxofunctionalization of (-)-ambroxide with H2O2 in the presence of bioinspired honheme Mn complexes is reported. Adjusting the ligand architecture and absolute chirality, as well as tuning the reaction solvent, allows switching the catalysts’ selectivity between biosynthetic-like and bioorthogonal modes, thus directing the reaction towards either (+)-sclareolide or 2α-hydroxyambroxide, respectively. This opens the ways to 2,12-dihydroxyambroxide, 2α-hydroxysclareolide, ambroxide-2-one, ambroxide-2,12-dione, and several other, including previously unavailable, oxidized metabolites of (-)-ambroxide in synthetically meaningful yields, using the same catalyst systems.

KW - Biomimetic chemistry

KW - C–H activation

KW - Late-stage functionalization

KW - Natural products

KW - Steroids

UR - http://www.scopus.com/inward/record.url?scp=85107021758&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2021.05.014

DO - 10.1016/j.jcat.2021.05.014

M3 - Article

AN - SCOPUS:85107021758

VL - 399

SP - 224

EP - 229

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -