Synthesis of C‐Oligosaccharides through Versatile C(sp3)−H Glycosylation of Glycosides DOI Creative Commons
Jun Wu,

Adelina Kopp,

Lutz Ackermann

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(11)

Published: Jan. 11, 2022

Abstract C‐ oligosaccharides are pharmacologically relevant because they more hydrolysis‐resistant than O ‐oligosaccharides. Despite indisputable advances, C ‐oligosaccharides continue to be underdeveloped, likely due a lack of efficient and selective strategies for the assembly interglycosidic C−C linkages. In contrast, we, herein, report versatile robust strategy synthesis structurally complex via catalyzed C(sp 3 )−H activations. Thus, wealth (2→1)‐ (1→1)‐ becomes readily available by palladium‐catalyzed glycoside glycosylation. The isolation key palladacycle intermediates experiments with isotopically‐labeled compounds identified trans‐ stereoselectivity activation manifold was likewise exploited diversification furanoses, pyranoses disaccharides.

Language: Английский

C–H activation DOI
Torben Rogge, Nikolaos Kaplaneris, Naoto Chatani

et al.

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

Citations

435
Toolbox for Distal C–H Bond Functionalizations in Organic Molecules DOI

Soumya Kumar Sinha,

Srimanta Guin,

Sudip Maiti

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

Citations

380
Transition-Metal-Catalyzed, Coordination-Assisted Functionalization of Nonactivated C(sp3)–H Bonds DOI
Bin Liu, Andrew M. Romine, Camille Rubel

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(24), P. 14957 - 15074

Published: Oct. 29, 2021

Transition-metal-catalyzed, coordination-assisted C(sp3)–H functionalization has revolutionized synthetic planning over the past few decades as use of these directing groups allowed for increased access to many strategic positions in organic molecules. Nonetheless, several challenges remain preeminent, such requirement high temperatures, difficulty removing or converting groups, and, although metals provide some reactivity, employing outside palladium. This review aims give a comprehensive overview coordination-assisted, transition-metal-catalyzed, direct nonactivated bonds by covering literature since 2004 order demonstrate current state-of-the-art methods well limitations. For clarity, this been divided into nine sections transition metal catalyst with subdivisions type bond formation. Synthetic applications and reaction mechanism are discussed where appropriate.

Language: Английский

Citations

367
Transition-Metal-Catalyzed C–H Bond Activation for the Formation of C–C Bonds in Complex Molecules DOI Creative Commons
Jamie H. Docherty,

Thomas M. Lister,

Gillian McArthur

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(12), P. 7692 - 7760

Published: May 10, 2023

Site-predictable and chemoselective C–H bond functionalization reactions offer synthetically powerful strategies for the step-economic diversification of both feedstock fine chemicals. Many transition-metal-catalyzed methods have emerged selective activation bonds. However, challenges regio- chemoselectivity with application to highly complex molecules bearing significant functional group density diversity. As molecular complexity increases within structures risks catalyst intolerance limited applicability grow number groups potentially Lewis basic heteroatoms. Given abundance bonds already diversified such as pharmaceuticals, natural products, materials, design selection reaction conditions tolerant catalysts has proved critical successful direct functionalization. such, innovations formation carbon–carbon been discovered developed overcome these limitations. This review highlights progress made metal-catalyzed C–C forming including alkylation, methylation, arylation, olefination targets.

Language: Английский

Citations

228
Stereodynamic Strategies to Induce and Enrich Chirality of Atropisomers at a Late Stage DOI
Casey B. Roos, Chang-Hwa Chiang, Lauren A. M. Murray

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(17), P. 10641 - 10727

Published: Aug. 28, 2023

Enantiomers, where chirality arises from restricted rotation around a single bond, are atropisomers. Due to the unique nature of origins their chirality, synthetic strategies access these compounds in an enantioselective manner differ those used prepare enantioenriched containing point arising unsymmetrically substituted carbon center. In particular stereodynamic transformations, such as dynamic kinetic resolutions, thermodynamic and deracemizations, which rely on ability racemize or interconvert enantiomers, promising set transformations optically pure late stage sequence. Translation approaches with atropisomers requires expanded toolbox for epimerization/racemization provides opportunity develop new conceptual framework synthesis compounds.

Language: Английский

Citations

51
Late-stage functionalization of peptides via a palladium-catalyzed C(sp3)–H activation strategy DOI
Bei‐Bei Zhan,

Meng‐Xue Jiang,

Bing‐Feng Shi

et al.

Chemical Communications, Journal Year: 2020, Volume and Issue: 56(90), P. 13950 - 13958

Published: Jan. 1, 2020

Peptides hold great promise in proteomics, diagnostics and drug discovery. While natural peptides continue to be of key importance, chemically modified unnatural have been found show enhanced biological activities improved therapeutic capabilities compared their counterparts. Therefore, the development efficient versatile strategies enable easy access is high demand. In recent years, palladium-catalyzed direct functionalization inert C(sp3)-H bonds has emerged as a powerful straightforward synthetic strategy for late-stage modification peptides. this review, we summarize progress emerging field. For clarity, review organized into three sections according peptide side-chains at β-, γ-, δ-positions.

Language: Английский

Citations

86
Emerging Organometallic Methods for the Synthesis of C‐Branched (Hetero)aryl, Alkenyl, and Alkyl Glycosides: C−H Functionalization and Dual Photoredox Approaches DOI
Juba Ghouilem,

Morgane de Robichon,

Franck Le Bideau

et al.

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(2), P. 491 - 511

Published: Aug. 28, 2020

Abstract Transition‐metal‐catalyzed C−H functionalization and photoredox nickel dual catalysis have emerged as innovative powerful avenues for the synthesis of C‐branched glycosides. These two concepts been recently established provide efficient mild methods accessing a series valuable complex glycosides great interest. Herein, recent developments in aryl/alkenyl/alkyl through these approaches are highlighted.

Language: Английский

Citations

73
Peptide Late-Stage Diversifications by Rhodium-Catalyzed Tryptophan C7 Amidation DOI Creative Commons
Wei Wang, Jun Wu, Rositha Kuniyil

et al.

Chem, Journal Year: 2020, Volume and Issue: 6(12), P. 3428 - 3439

Published: Nov. 20, 2020

Language: Английский

Citations

72
Late‐Stage Peptide Macrocyclization by Palladium‐Catalyzed Site‐Selective C−H Olefination of Tryptophan DOI

Zengbing Bai,

Chuangxu Cai,

Wangjian Sheng

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(34), P. 14686 - 14692

Published: June 8, 2020

Transition-metal-catalyzed C-H activation has shown potential in the functionalization of peptides with expanded structural diversity. Herein, development late-stage peptide macrocyclization methods by palladium-catalyzed site-selective C(sp2 )-H olefination tryptophan residues at C2 and C4 positions is reported. This strategy utilizes backbone as endogenous directing groups provides access to macrocycles unique Trp-alkene crosslinks.

Language: Английский

Citations

71
Stereoselective Synthesis of C‐Vinyl Glycosides via Palladium‐Catalyzed C−H Glycosylation of Alkenes DOI
Qikai Sun, Huixing Zhang,

Quanquan Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(36), P. 19620 - 19625

Published: July 6, 2021

C-vinyl glycosides are an important class of carbohydrates and pose a unique synthetic challenge. A new strategy has been developed for stereoselective synthesis via Pd-catalyzed directed C-H glycosylation alkenes with glycosyl chloride donors using easily removable bidentate auxiliary. Both the γ bond allylamines δ homoallyl amine substrates can be glycosylated in high efficiency excellent regio- stereoselectivity. The resulting further converted to variety C-alkyl stereospecificity. These reactions offer broadly applicable method streamline complex from accessible starting materials.

Language: Английский

Citations

68