Ligand‐Controlled Stereoselective Synthesis of 2‐Deoxy‐β‐C‐glycosides by Cobalt Catalysis DOI

Bingxue Liu,

Deguang Liu, Xianle Rong

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(22)

Published: March 17, 2023

2-Deoxy-β-C-glycosides represent an important class of carbohydrates that are present in many bioactive molecules. However, owing to the lack substituents at C2 position, stereoselective synthesis 2-deoxy-β-C-glycosides is highly challenging. Herein, we report a ligand-controlled C-alkyl glycosylation reaction access 2-deoxy-β-C-alkyl glycosides from readily available glycals and alkyl halides. This method exhibits broad substrate scope excellent diastereoselectivity under very mild conditions. In addition, unprecedented stereodivergent 2-deoxy-C-ribofuranosides achieved using different chiral bisoxazoline ligands. Mechanistic studies suggest hydrometallation glycal with bisoxazoline-ligated Co-H species may be turnover-limiting stereodetermining step this transformation.

Language: Английский

Nontraditional Fragment Couplings of Alcohols and Carboxylic Acids: C(sp3)–C(sp3) Cross-Coupling via Radical Sorting DOI
Holt A. Sakai, David W. C. MacMillan

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(14), P. 6185 - 6192

Published: March 30, 2022

Alcohols and carboxylic acids are among the most commercially abundant, synthetically versatile, operationally convenient functional groups in organic chemistry. Under visible light photoredox catalysis, these native synthetic handles readily undergo radical activation, resulting open-shell intermediates can subsequently participate transition metal catalysis. In this report, we describe C(sp3)–C(sp3) cross-coupling of alcohols through dual combination N-heterocyclic carbene (NHC)-mediated deoxygenation hypervalent iodine-mediated decarboxylation. This mild practical Ni-catalyzed radical-coupling protocol was employed to prepare a wide array alkyl–alkyl cross-coupled products, including highly congested quaternary carbon centers from corresponding tertiary or acids. We demonstrate applications methodology alcohol C1-alkylation formal homologation, as well late-stage functionalization drugs, natural biomolecules.

Language: Английский

Citations

149
Iron-catalysed reductive cross-coupling of glycosyl radicals for the stereoselective synthesis of C-glycosides DOI Open Access

Quanquan Wang,

Qikai Sun, Yi Jiang

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(3), P. 235 - 244

Published: Feb. 17, 2022

Language: Английский

Citations

84
Visible light activation enables desulfonylative cross-coupling of glycosyl sulfones DOI

Quanquan Wang,

Boon Chong Lee,

Ting Jun Tan

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 1(12), P. 967 - 974

Published: Sept. 22, 2022

Language: Английский

Citations

77
Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO2 via Photoredox Catalysis DOI
Wen‐Duo Li, Yang Wu, Shijun Li

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(19), P. 8551 - 8559

Published: April 4, 2022

A new strategy for the direct cleavage of C(sp3)-OH bond has been developed via activation free alcohols with neutral diphenyl boryl radical generated from sodium tetraphenylborate under mild visible light photoredox conditions. This verified by cross-electrophile coupling and carbon dioxide synthesis carboxylic acids. Direct transformation a range primary, secondary, tertiary benzyl to acids achieved. Control experiments computational studies indicate that undergoes homolysis bond, generating alkyl radicals. After reducing into anion conditions, following carboxylation CO2 affords product.

Language: Английский

Citations

70
Direct synthesis of unprotected aryl C-glycosides by photoredox Ni-catalysed cross-coupling DOI
Chen Zhang,

Shiyang Xu,

Hao Zuo

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(3), P. 251 - 260

Published: Jan. 16, 2023

Language: Английский

Citations

69
Diversification of Glycosyl Compounds via Glycosyl Radicals DOI Creative Commons
Yi Jiang, Yijun Zhang,

Boon Chong Lee

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(38)

Published: June 7, 2023

Glycosyl radical functionalization is one of the central topics in synthetic carbohydrate chemistry. Recent advances metal-catalyzed cross-coupling chemistry and metallaphotoredox catalysis provided powerful platforms for glycosyl diversification. In particular, discovery new precursors conjunction with these advanced reaction technologies have significantly expanded space compound synthesis. this Review, we highlight most recent progress area starting from 2021, reports included will be categorized based on different types better clarity.

Language: Английский

Citations

66
Carbon-centered radical capture at nickel(II) complexes: Spectroscopic evidence, rates, and selectivity DOI Creative Commons
Qiao Lin, Ethan Spielvogel, Tianning Diao

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(5), P. 1295 - 1308

Published: March 13, 2023

Language: Английский

Citations

65
Radical Pathway Glycosylation Empowered by Bench-Stable Glycosyl Donors DOI
Weidong Shang, Dawen Niu

Accounts of Chemical Research, Journal Year: 2023, Volume and Issue: 56(18), P. 2473 - 2488

Published: Aug. 18, 2023

ConspectusThe study of carbohydrates has emerged as a crucial research area in various disciplines due to their pivotal roles cellular processes. To facilitate in-depth exploration biological functions, chemical glycosylation reactions that allow facile access glycoconjugates broad community are highly needed. In classical reactions, glycosyl donor is activated by an acid generate reactive electrophilic intermediate, which subsequently forms glycosidic bond upon reaction with nucleophilic acceptor. Such ionic pathway been the mainstay technique for glycoconjugate synthesis and allowed numerous intricate structures. Nevertheless, limitations still exist. For instance, when labile donors or harsh activating conditions required, these methods show limited tolerance hydroxyl groups abundant on sugar rings. addition, achieving good stereocontrol represents another longstanding obstacle. recent years, new modes activation have sought tackle above challenges.We noted passing through intermediacy radicals via cascade single-electron transfer steps possess significant but underexplored potential. Progress this slow large part dearth handy maneuver radicals. Most existing call either forcing unstable/inconvenient starting materials. order better exploit power radical glycosylation, we developed range donors─namely, sulfoxides, sulfones, sulfinates─that bench stable can be readily prepared from simple These form under mild conditions. Enabled use donors, series could used making O-, S-, C-glycosides, some were previously difficult access. many cases, no protecting group required. As illustration potential utility, our adopted preparation sugar–drug conjugates, sugar–DNA glycopeptides, even glycoproteins. While most cases intrinsic reactivity intermediates explored axially configured products, also utilization external, delicate reagents, catalysts override such innate preference achieve catalyst-controlled stereoselectivity.We believe enormous inspire development novel glycoside synthesis. Account, highlight design principles summarize advancements enabled use, provide outlook future directions field.

Language: Английский

Citations

57
Direct radical functionalization of native sugars DOI Creative Commons
Yi Jiang, Yi Wei, Qianyi Zhou

et al.

Nature, Journal Year: 2024, Volume and Issue: 631(8020), P. 319 - 327

Published: June 19, 2024

Abstract Naturally occurring (native) sugars and carbohydrates contain numerous hydroxyl groups of similar reactivity 1,2 . Chemists, therefore, rely typically on laborious, multi-step protecting-group strategies 3 to convert these renewable feedstocks into reagents (glycosyl donors) make glycans. The direct transformation native complex saccharides remains a notable challenge. Here we describe photoinduced approach achieve site- stereoselective chemical glycosylation from widely available sugar building blocks, which through homolytic (one-electron) chemistry bypasses unnecessary group masking manipulation. This process is reminiscent nature in its regiocontrolled generation transient glycosyl donor, followed by radical-based cross-coupling with electrophiles activation light. Through selective anomeric functionalization mono- oligosaccharides, this protecting-group-free ‘cap glycosylate’ offers straightforward access wide array metabolically robust compounds. Owing biocompatibility, the method was extended post-translational proteins.

Language: Английский

Citations

35
Transformations of carbohydrate derivatives enabled by photocatalysis and visible light photochemistry DOI Creative Commons

Daniel J. Gorelik,

Shrey P. Desai,

Sofia Jdanova

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(4), P. 1204 - 1236

Published: Jan. 1, 2024

This review article highlights the diverse ways in which recent developments areas of photocatalysis and visible light photochemistry are impacting synthetic carbohydrate chemistry.

Language: Английский

Citations

29