Harnessing Bromo/Acyloxy Transposition (BrAcT) and Excited-State Copper Catalysis for Styrene Difunctionalization DOI
Upasana Mukherjee, Jagrut Shah, Djamaladdin G. Musaev

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(31), P. 21271 - 21279

Published: July 23, 2024

1,2-Difunctionalization of styrenes, adding two distinct functional groups across the C═C double bond, has emerged as a powerful tool for enhancing molecular complexity. Herein, we report development regioconvergent β-acyloxylation-α-ketonylation styrenes through bromo/acyloxy transposition (BrAcT) and excited-state copper catalysis. This approach is amenable to gram-scale synthesis tolerates wide range complex frameworks, including derivatives natural products marketed drugs. Our experimental computational studies suggest unique mechanism featuring dynamic, ionic BrAcT process copper-catalyzed redox reactions. We anticipate that this could serve broadly applicable versatile strategy β-acyloxylation-α-functionalization creating valuable intermediates preparing new pharmaceuticals, agrochemicals, materials.

Language: Английский

Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications DOI
Mu‐Jia Luo, Qiang Xiao, Jin‐Heng Li

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(16), P. 7206 - 7237

Published: Jan. 1, 2022

This review covers the recent progress in electro-/photo-catalytic alkene-derived radical cation chemistry for organic synthesis, including synthetic strategies, plausible mechanisms and further research outlook.

Language: Английский

Citations

141
Radical Hydrocarboxylation of Unactivated Alkenes via Photocatalytic Formate Activation DOI
Sara N. Alektiar, Jimin Han, Yun Dang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(20), P. 10991 - 10997

Published: May 15, 2023

Herein we disclose a strategy to promote the hydrocarboxylation of unactivated alkenes using photochemical activation formate salts. We illustrate that an alternative initiation mechanism circumvents limitations prior approaches and enables this challenging substrate class. Specifically, found accessing requisite thiyl radical initiator without exogenous chromophore eliminates major byproducts have plagued attempts exploit similar reactivity for alkene substrates. This redox-neutral method is technically simple execute effective across broad range Feedstock alkenes, such as ethylene, are hydrocarboxylated at ambient temperature pressure. A series cyclization experiments indicate how described in report can be diverted by more complex processes.

Language: Английский

Citations

62
Arylthianthrenium Salts as the Aryl Sources: Visible Light/Copper Catalysis-Enabled Intermolecular Azidosulfonylation of Alkenes DOI
Hao Xu, Xufeng Li, Yifei Wang

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(9), P. 1845 - 1850

Published: Feb. 26, 2024

The difunctionalization of alkenes using aryl thianthrenium salts as the sources has been reported sporadically. However, four-component on basis not thus far and still remains a challenge. Herein, visible light/copper catalysis-enabled reaction salts, DABCO·(SO

Language: Английский

Citations

23
An iron-catalyzed multicomponent reaction of cycloketone oxime esters, alkenes, DABCO·(SO2)2 and trimethylsilyl azide DOI
Jun Zhang,

Junwei Wu,

Xiaotong Chang

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(4), P. 917 - 922

Published: Jan. 1, 2022

The synthesis of β-azidosulfones starting from alkenes, cycloketone oxime esters, trimethylsilyl azide and a sulfur dioxide surrogate DABCO·(SO 2 ) under iron catalysis is developed.

Language: Английский

Citations

44
Salt‐Stabilized Silylzinc Pivalates for Nickel‐Catalyzed Carbosilylation of Alkenes DOI
Jixin Wang,

Zhili Duan,

Xingchen Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)

Published: Feb. 18, 2022

Abstract We herein report the preparation of solid and salt‐stabilized silylzinc pivalates from corresponding silyllithium reagents via transmetalation with Zn(OPiv) 2 . These resulting organosilylzinc show enhanced air moisture stability unique reactivity in silylative difunctionalization alkenes. Thus, a practical chelation‐assisted nickel‐catalyzed regioselective alkyl benzylsilylation alkenes has been developed, which provides an easy method to access silanes broad substrate scope wide functional group compatibility. Kinetic experiments highlight that OPiv‐coordination is crucial improve pivalates. Furthermore, late‐stage functionalizations druglike molecules versatile modifications products illustrate synthetical utility this protocol.

Language: Английский

Citations

44
N-Amino pyridinium salts in organic synthesis DOI
Pritam Roychowdhury, Samya Samanta, Hao Tan

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(10), P. 2563 - 2580

Published: Jan. 1, 2023

This review summarizes the synthesis and reactivity of N -aminopyridinium salts, discusses applications in organic synthesis, highlights potential for these reagents to enable novel synthetic disconnections innovations.

Language: Английский

Citations

40
Regiospecific Alkene Aminofunctionalization via an Electrogenerated Dielectrophile DOI
Dylan E. Holst, Céline Dorval,

Casey K. Winter

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(15), P. 8299 - 8307

Published: April 6, 2023

Modular strategies to rapidly increase molecular complexity have proven immensely synthetically valuable. In principle, transformation of an alkene into a dielectrophile presents opportunity deliver two unique nucleophiles across alkene. Unfortunately, the selectivity profiles known dielectrophiles largely precluded this deceptively simple synthetic approach. Herein, we demonstrate that dicationic adducts generated through electrolysis alkenes and thianthrene possess profile relative more conventional dielectrophiles. Specifically, these species undergo single perfectly regioselective substitution reaction with phthalimide salts. This observation unlocks appealing new platform for aminofunctionalization reactions. As illustrative example, implement reactivity paradigm address longstanding challenge: diamination distinct nitrogen nucleophiles. Studies mechanism process reveal key alkenyl thianthrenium salt intermediate controls exquisite regioselectivity highlight importance proton sources in controlling sulfonium electrophiles.

Language: Английский

Citations

34
Photoredox radical/polar crossover enables C–H gem-difunctionalization of 1,3-benzodioxoles for the synthesis of monofluorocyclohexenes DOI Creative Commons
Jiabao Tian, Lei Zhou

Chemical Science, Journal Year: 2023, Volume and Issue: 14(22), P. 6045 - 6051

Published: Jan. 1, 2023

A photocatalytic C-H gem-difunctionalization of 1,3-benzodioxoles with two different alkenes for the synthesis highly functionalized monofluorocyclohexenes is described. Using 4CzIPN as photocatalyst, direct single electron oxidation allows their defluorinative coupling α-trifluoromethyl to produce gem-difluoroalkenes in a redox-neutral radical polar crossover manifold. The bond resultant γ,γ-difluoroallylated was further via addition electron-deficient using more oxidizing iridium photocatalyst. capture situ generated carbanions by an electrophilic gem-difluoromethylene carbon and consecutive β-fluoride elimination afford monofluorocyclohexenes. synergistic combination multiple termination pathways enables rapid incorporation molecular complexity stitching simple readily accessible starting materials together.

Language: Английский

Citations

34
Alkene Thianthrenation Unlocks Diverse Cation Synthons: Recent Progress and New Opportunities DOI Creative Commons
Min Ji Kim, Karina Targos, Dylan E. Holst

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 8, 2024

Oxidative alkene functionalization reactions are a fundamental class of complexity-building organic transformations. However, the majority established approaches rely on electrophilic reagents that limit diversity groups can be installed. Recent advances have new approach instead relies transformation alkenes into thianthrene-derived cationic electrophiles. These linchpin intermediates generated selectively and undergo diverse array mechanistically distinct with abundant nucleophiles. Taken together, this unlocks suite net oxidative transformations been elusive using conventional strategies. This Minireview describes these is organized around three synthons formally accessible from via thianthrenation: 1) alkenyl cations; 2) vicinal dications; 3) allyl cations. Throughout Minireview, we illustrate how thianthrenium salts address key limitations endemic to classic alkene-derived electrophiles highlight mechanistic origins distinctions wherever possible.

Language: Английский

Citations

9
Copper-Catalyzed Selective Amino-alkoxycarbonylation of Unactivated Alkenes with CO DOI Creative Commons

Si‐Shun Yan,

Ralf Jackstell, Matthias Beller

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

1,2-Amino-difunctionalization reactions of alkenes allow the efficient introduction different functional groups and rapid construction valuable functionalized amines. In this respect, we report a copper-catalyzed 1,2-amino-alkoxycarbonylation unactivated with CO alkylamine precursors in presence Lewis acid additive. The novel protocol allows direct access to β-amino derivatives from easily available starting materials. presented methods feature high chemo- regioselectivities, good group tolerance, substrate scope including diverse bioactive compounds drug-like molecules. Mechanistic studies indicate that additive is key realizing umpolung addition nucleophilic aminyl radicals electron-rich alkenes, which represents an elegant activation strategy for radicals.

Language: Английский

Citations

1