Iridium-Catalyzed Migratory Terminal C(sp3)–H Amidation of Heteroatom-Substituted Internal Alkenes via Olefin Chain Walking DOI
Qing Wang, Hoimin Jung, Dongwook Kim

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 31, 2023

Hydroamination facilitated by metal hydride catalysis is an appealing synthetic approach to access valuable nitrogen-containing compounds from readily available unsaturated hydrocarbons. While high regioselectivity can be achieved usually for substrates bearing polar chelation groups, the reaction involving simple alkenes frequently provides nonselective outcomes. Herein, we report iridium-catalyzed highly regioselective terminal C(sp3)-H amidation of internal utilizing dioxazolones as amino source via olefin chain walking. Most notably, this mechanistic motif double bond migration position operates not only with dialkyl-substituted including styrenes but also heteroatom-substituted olefins such enol ethers, vinyl silanes, and borons, thus representing first example methyl latter type through a nondissociative walking process.

Language: Английский

Light-empowered contra-thermodynamic stereochemical editing DOI

Peng‐Zi Wang,

Wen‐Jing Xiao, Jia‐Rong Chen

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 7(1), P. 35 - 50

Published: Nov. 16, 2022

Language: Английский

Citations

79
Biomimetic 1,2-amino migration via photoredox catalysis DOI Creative Commons

Wei‐Tai Fan,

Yuang Cui,

Bei‐Bei Zhan

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Synthetic organic chemists continually draw inspiration from biocatalytic processes to innovate synthetic methodologies beyond existing catalytic platforms. Within this context, although 1,2-amino migration represents a viable biochemical process, it remains underutilized within the chemistry community. Here we present biomimetic accomplished through synergistic combination of mechanism and photoredox catalysis. This platform enables modular synthesis γ-substituted β-amino acids by utilizing abundant α-amino-acid derivatives readily available molecules as coupling partners. mild method features excellent substrate functionality compatibility, affording diverse range (more than 80 examples) without need for laborious multistep synthesis. Mechanistic studies, supported both experimental observations theoretical analysis, indicate that involves radical addition α-vinyl-aldimine ester, 3-exo-trig cyclization subsequent rearrangement process. We anticipate transformation will serve versatile highly efficient construction unnatural acids. Enzyme-catalysed process is currently Building upon mechanism, photoredox-catalysed has been developed. By integrating conditions, approach library

Language: Английский

Citations

4
Asymmetric 1,4-functionalization of 1,3-enynes via dual photoredox and chromium catalysis DOI Creative Commons
Feng‐Hua Zhang,

Xiaochong Guo,

Xianrong Zeng

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Aug. 26, 2022

Abstract The merger of photoredox and transition-metal catalysis has evolved as a robust platform in organic synthesis over the past decade. stereoselective 1,4-functionalization 1,3-enynes, prevalent synthon synthetic chemistry, could afford valuable chiral allene derivatives. However, tremendous efforts have been focused on ionic reaction pathway. radical-involved asymmetric 1,3-enynes remains prominent challenge. Herein, we describe three-component 1,4-dialkylation via dual chromium to provide allenols. This method features readily available starting materials, broad substrate scope, good functional group compatibility, high regioselectivity, simultaneous control axial central chiralities. Mechanistic studies suggest that this proceeds through redox-neutral

Language: Английский

Citations

70
Energy- and atom-efficient chemical synthesis with endergonic photocatalysis DOI
Huaiju Wang, Ya‐Ming Tian,

Burkhard König

et al.

Nature Reviews Chemistry, Journal Year: 2022, Volume and Issue: 6(10), P. 745 - 755

Published: Sept. 23, 2022

Language: Английский

Citations

64
Functional-group translocation of cyano groups by reversible C–H sampling DOI
K. Chen,

Qingrui Zeng,

L. XIE

et al.

Nature, Journal Year: 2023, Volume and Issue: 620(7976), P. 1007 - 1012

Published: June 26, 2023

Language: Английский

Citations

43
Ratcheting synthesis DOI
Stefan Borsley, James Gallagher, David A. Leigh

et al.

Nature Reviews Chemistry, Journal Year: 2023, Volume and Issue: 8(1), P. 8 - 29

Published: Dec. 15, 2023

Language: Английский

Citations

32
Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization DOI
Xinghua Wang,

J. P. He,

Yanan Wang

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

Citations

16
Endergonic synthesis driven by chemical fuelling DOI Creative Commons
Enzo Olivieri, James Gallagher, Alexander Betts

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(6), P. 707 - 714

Published: March 11, 2024

Abstract Spontaneous chemical reactions proceed energetically downhill to either a local or global minimum, limiting possible transformations those that are exergonic. Endergonic do not spontaneously and require an input of energy. Light has been used drive number deracemizations thermodynamically unfavourable bond-forming reactions, but is restricted substrates can absorb, directly indirectly, energy provided by photons. In contrast, anabolism involves uphill powered fuels. Here we report on the transduction from artificial fuel Diels–Alder reaction. Carboxylic acid catalysed carbodiimide-to-urea formation chemically orthogonal reaction diene dienophile, transiently brings functional groups into close proximity, causing otherwise prohibited cycloaddition in modest yield (15% after two fuelling cycles) with high levels regio- (>99%) stereoselectivity (92:8 exo : endo ). Kinetic asymmetry cycle ratchets away equilibrium distribution Diels–Alder:retro-Diels–Alder products. The driving endergonic occurs through ratchet mechanism (an information ratchet, depending synthetic protocol), reminiscent how molecular machines directionally bias motion. Ratcheting synthesis potential expand chemistry toolbox terms reactivity, complexity control.

Language: Английский

Citations

14
(Z)-Selective Isomerization of 1,1-Disubstituted Alkenes by Scandium-Catalyzed Allylic C–H Activation DOI
Shao‐Jie Lou, Pan Wang, Xin Wen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(39), P. 26766 - 26776

Published: Sept. 20, 2024

The isomerization of 1,1-disubstituted alkenes through 1,3-hydrogen shift is an atom-efficient route for synthesizing trisubstituted alkenes, which are important moieties in many natural products, pharmaceuticals, and organic materials. However, this reaction often encounters regio- stereoselectivity challenges, typically yielding

Language: Английский

Citations

8
Organic Synthesis Away from Equilibrium: Contrathermodynamic Transformations Enabled by Excited-State Electron Transfer DOI
A. T. Lin, Sumin Lee, Robert R. Knowles

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(13), P. 1827 - 1838

Published: June 21, 2024

ConspectusChemists have long been inspired by biological photosynthesis, wherein a series of excited-state electron transfer (ET) events facilitate the conversion low energy starting materials such as H

Language: Английский

Citations

7