首页|Excited-State Palladium-Catalyzedα-Selective C1-Ketonylation

Excited-State Palladium-Catalyzedα-Selective C1-Ketonylation

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C-Glycosides are important carbohydrate mimetics found in natural products,bioactive compounds,and marketed drugs.However,stereoselective preparation of this class of glycomimetics remains a significant challenge in organic synthesis.Herein,we report an excited-state palladium-catalyzed α-selective C-ketonylation synthetic strategy using readily avail-able 1-bromosugars to access a range of C-glycosides.The reaction featured excellent α-selectivity and mild conditions that tolerated a wide range of functional groups and complex molecular architectures.The resulting α-ketonylsugars could serve as versatile pre-cursors for their β-isomers and other C-glycosides.Preliminary experimental and computational studies of the mechanism suggested a radical pathway involv-ing the formation of palladoradical and glycosyl radi-cal that undergoes polarity-mismatched coupling with silyl enol ether,affording the desired α-ketonylsugars.Insight into the reactivity and mechanism will inspire a new reaction development and provide straightfor-ward access to both α-and β-C-glycosides,thereby greatly expanding the chemical and patent spaces of glycomimetics.

excited-state catalysispalladiumglycosyl radicalketonylationsilyl enol ethers

Gaoyuan Zhao、Upasana Mukherjee、Lin Zhou、Jaclyn N.Mauro、Yue Wu、Peng Liu、Ming-Yu Ngai

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Department of Chemistry,Institute of Chemical Biology and Drug Discovery,State University of New York at Stony Brook,Stony Brook,New York 11794

Department of Chemistry,University of Pittsburgh,Pittsburgh,Pennsylvania 15260

Department of Chemical and Petroleum Engineering,University of Pittsburgh,Pittsburgh,Pennsylvania 15260

美国国立卫生研究院项目美国国立卫生研究院项目National Science Foundation,VA,USANational Institute of General Medical Sciences(NIGMS;MD,USA)equipment administrative supplementShimadzu Scientific Instruments grantOffice of the Vice President for Research at Stony Brook University,NY,USA

R35-GM119652R35-GM128779ACl1548562R35-GM119652-04S1

2023

10.31635/ccschem.022.202202282

中国化学会会刊(英文)

中国化学会会刊(英文)

CSCD
ISSN：
年,卷(期)：2023.5(1)
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