Palladium-catalyzed C-H Glycosylation and Retro Diels-Alder Tandem Reaction Structurally Modified Norbornadienes (smNBDs)

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Nov 8

PMID 34745545

Citations 6

Authors

Yang An

Bo-Sheng Zhang

Ya-Nan Ding

Zhe Zhang

Xue-Ya Gou

Xue-Song Li

Xiaolei Wang

Yuke Li

Yong-Min Liang

Affiliations

Soon will be listed here.

Abstract

This report describes palladium-catalyzed C-H glycosylation and retro Diels-Alder tandem reaction structurally modified norbornadienes (smNBDs). smNBDs were proposed to regulate the reactivity of the aryl-norbornadiene-palladacycle (ANP), including its high chemoselectivity and regioselectivity, which were the key to constructing C2 and C3 unsubstituted C4-glycosidic indoles. The scope of this substrate is extensive; the halogenated six-membered and five-membered glycosides were applied to the reaction smoothly, and -alkyl (primary, secondary and tertiary) C4-glycosidic indoles can also be obtained by this method. In terms of mechanism, the key ANP intermediates characterized by X-ray single-crystal diffraction and further controlled experiments proved that the migration-insertion of smNBDs with phenylpalladium intermediate endows them with high chemo- and regioselectivity. Finally, density functional theory (DFT) calculation further verified the rationality of the mechanism.

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