Catalytic Multicomponent Synthesis ofC‐Acyl Glycosides by Consecutive Cross‐Electrophile Couplings DOI
Yi Jiang,

Kai Yang,

Yi Wei

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 27, 2022

C-Acyl glycosides are versatile intermediates to natural products and medicinally relevant entities. Conventional cross-coupling strategies secure these molecules often relied on two-component manifolds in which a glycosyl precursor is coupled with an acyl donor (pre-synthesized or generated situ) under transition metal dual catalysis forge C-C bond. Here, we disclose three-component Ni-catalyzed reductive regime that facilitates the chemoselective union of halides, organoiodides commercially available isobutyl chloroformate as CO surrogate. The method tolerates multiple functionalities resulting obtained high diastereoselectivities. Theoretical calculations provide mechanistic rationale for unexpectedly chemoselectivity sequential cross-electrophile couplings. This approach enables expeditious assembly difficult-to-synthesize C-acyl glycosides, well late-stage keto-glycosylation oligopeptides.

Language: Английский

Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel DOI
Shengqing Zhu, Xian Zhao, Huan Li

et al.

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(19), P. 10836 - 10856

Published: Jan. 1, 2021

The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction complex motifs. Despite remarkable progress, novel and efficient methods achieving such transformations under milder conditions with chemo-, regio-, stereoselectivity still remain significant challenge; thus, their development is highly desirable. Recently, merging nickel catalysis radical chemistry offers new benign unprecedented reactivity selectivity. In this review, we summarize recent advances in area by underpinning domino involving capture to provide clear overview reaction designs mechanistic scenarios.

Language: Английский

Citations

248
Transition Metal (Ni, Cu, Pd)-Catalyzed Alkene Dicarbofunctionalization Reactions DOI

Laura M. Wickham,

Ramesh Giri

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 54(17), P. 3415 - 3437

Published: Aug. 12, 2021

ConspectusRecently, alkene dicarbofunctionalization, i.e., the powerful organic synthesis method of difunctionalization with two carbon sources, emerged as a formidable reaction immense promise to synthesize complex molecules expeditiously from simple chemicals. This is generally achieved transition metals (TMs) through interception by sources an alkylmetal [β-H–C(sp3)–[M]] species, key intermediate prone undergo rapid β-H elimination. Related prior reports, since Paolo Chiusoli and Catellani's work in 1982 [ Tetrahedron Lett. 1982, 23, 4517], have used bicyclic disubstituted terminal alkenes, wherein elimination avoided geometric restriction or complete lack β-H's. With reasoning that β-H–C(sp3)–[M] intermediates could be rendered amenable use first row late TMs formation coordination-assisted transient metallacycles, these strategies were implemented address problem dicarbofunctionalization reactions.Because catalyze C(sp3)–C(sp3) coupling, Cu Ni anticipated impart sufficient stability intermediates, generated catalytically upon carbometalation, for their subsequent electrophiles/nucleophiles three-component reactions. Additionally, such innate property enable coupling partners entropically driven cyclization/coupling The cyclometalation concept stabilize intractable was hypothesized when reactions performed. idea curtail founded Whitesides's J. Am. Chem. Soc. 1976, 98, 6521] observation metallacycles much slower than acyclic alkylmetals.In this Account, examples demonstrate catalysts alkenylzinc reagents, alkyl halides, aryl halides afford carbo- heterocycles. In addition, forming nickellacycles enabled regioselective performance various alkenyl compounds. situ [M]-H alkenes after induced unprecedented metallacycle contraction process, which six-membered metal-containing rings shrank five-membered cycles, allowing creation new carbon–carbon bonds at allylic (1,3) positions. Applications are discussed.

Language: Английский

Citations

236
Dual Nickel/Photoredox-Catalyzed Asymmetric Carbosulfonylation of Alkenes DOI Creative Commons
Xiaoyong Du, Iván Cheng‐Sánchez, Cristina Nevado

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(23), P. 12532 - 12540

Published: May 30, 2023

An asymmetric three-component carbosulfonylation of alkenes is presented here. The reaction, involving the simultaneous formation a C-C and C-S bond across π-system, uses dual nickel/photoredox catalytic system to produce both β-aryl β-alkenyl sulfones in high yields with excellent levels stereocontrol (up 99:1 er). This protocol exhibits broad substrate scope functional group tolerance its synthetic potential has been demonstrated by successful applications toward pharmacologically relevant molecules. A array control experiments supports involvement secondary alkyl radical intermediate generated through addition sulfonyl double bond. Moreover, stoichiometric cross-over further suggest an underlying Ni(0)/Ni(I)/Ni(III) pathway operative these transformations.

Language: Английский

Citations

66
Alkene dialkylation by triple radical sorting DOI
Johnny Wang, William L. Lyon, David W. C. MacMillan

et al.

Nature, Journal Year: 2024, Volume and Issue: 628(8006), P. 104 - 109

Published: Feb. 13, 2024

Language: Английский

Citations

41
Carbon quaternization of redox active esters and olefins by decarboxylative coupling DOI
Xu-cheng Gan,

Benxiang Zhang,

Nathan Dao

et al.

Science, Journal Year: 2024, Volume and Issue: 384(6691), P. 113 - 118

Published: April 4, 2024

The synthesis of quaternary carbons often requires numerous steps and complex conditions or harsh reagents that act on heavily engineered substrates. This is largely a consequence conventional polar-bond retrosynthetic disconnections in turn require multiple functional group interconversions, redox manipulations, protecting chemistry. Here, we report simple catalyst reductant combination converts two types feedstock chemicals, carboxylic acids olefins, into tetrasubstituted through quaternization radical intermediates. An iron porphyrin activates each substrate by electron transfer hydrogen atom transfer, then combines the fragments using bimolecular homolytic substitution (S

Language: Английский

Citations

33
Iron-catalyzed fluoroalkylative alkylsulfonylation of alkenes via radical-anion relay DOI Creative Commons
Xiaoya Hou, Hongchi Liu, Hanmin Huang

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Feb. 17, 2024

Abstract Transition metal-catalyzed reductive difunctionalization of alkenes with alkyl halides is a powerful method for upgrading commodity chemicals into densely functionalized molecules. However, super stoichiometric amounts metal reductant and the requirement installing directing group to suppress inherent β-H elimination bring great limitations this type reaction. We demonstrate herein that two different accessible via radical-anion relay Na 2 S O 4 as both sulfone-source. The together electron-shuttle catalyst crucial divert mechanistic pathway toward formation sulfone anion instead previously reported alkylmetal intermediates. Mechanistic studies allow identification carbon-centered radical sulfur-centered radical, which are in equilibrium capture or extrusion SO could be converted accelerated by iron catalysis, leading observed high chemoselectivity.

Language: Английский

Citations

26
A Bimolecular Homolytic Substitution-Enabled Platform for Multicomponent Cross-Coupling of Unactivated Alkenes DOI
Fei Cong,

Guo‐Quan Sun,

Si‐Han Ye

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10274 - 10280

Published: April 3, 2024

The construction of C(sp3)–C(sp3) bonds remains one the most difficult challenges in cross-coupling chemistry. Here, we report a photoredox/nickel dual catalytic approach that enables simultaneous formation two linkages via trimolecular alkenes with alkyl halides and hypervalent iodine-based reagents. reaction harnesses bimolecular homolytic substitution (SH2) mechanism chemoselective halogen-atom transfer (XAT) to orchestrate regioselective addition electrophilic nucleophilic radicals across unactivated without need for directing auxiliary. Utility is highlighted through late-stage (fluoro)alkylation (trideutero)methylation C═C bearing different patterns, offering straightforward access drug-like molecules comprising sp3-hybridized carbon scaffolds.

Language: Английский

Citations

26
Cross-Electrophile Coupling: Principles, Methods, and Applications in Synthesis DOI Creative Commons
Lauren E. Ehehalt, Omar M. Beleh, Isabella C. Priest

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Cross-electrophile coupling (XEC), defined by us as the cross-coupling of two different σ-electrophiles that is driven catalyst reduction, has seen rapid progression in recent years. As such, this review aims to summarize field from its beginnings up until mid-2023 and provide comprehensive coverage on synthetic methods current state mechanistic understanding. Chapters are split type bond formed, which include C(sp

Language: Английский

Citations

25
Three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals DOI
Pin Gao,

Yue-Jie Niu,

Fan Yang

et al.

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(6), P. 730 - 746

Published: Dec. 8, 2021

This article provides a comprehensive perspective on three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals, which generated from structurally diverse electrophilic and nucleophilic precursors under mild conditions.

Language: Английский

Citations

81
Directing-group-free catalytic dicarbofunctionalization of unactivated alkenes DOI
Hongyu Wang,

Chen‐Fei Liu,

Robert T. Martin

et al.

Nature Chemistry, Journal Year: 2021, Volume and Issue: 14(2), P. 188 - 195

Published: Dec. 13, 2021

Language: Английский

Citations

73