Metallaphotoredox-Catalyzed Cross-Electrophile Csp3–Csp3 Coupling of Aliphatic Bromides DOI

Russell T. Smith,

Xiaheng Zhang, Juan A. Rincón

et al.

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(50), P. 17433 - 17438

Published: Dec. 5, 2018

A strategy for the installation of small alkyl fragments onto pharmaceutically relevant aliphatic structures has been established via metallaphotoredox catalysis. Herein, we report that tris(trimethylsilyl)silanol can be employed as an effective halogen abstraction reagent that, in combination with photoredox and nickel catalysis, allows a generic approach to Csp3–Csp3 cross-electrophile coupling. In this study, demonstrate variety drug-like groups successfully coupled number commercially available electrophiles, including methyl tosylate strained cyclic bromides. Moreover, union two secondary carbon centers, long-standing challenge organic molecule construction, accomplished wide array structural formats. Last, technology selectively merged Csp2–Csp3 aryl–alkyl couplings build systems highly modular fashion.

Language: Английский

Aryl Sulfonium Salts for Site‐Selective Late‐Stage Trifluoromethylation DOI Creative Commons
Fei Ye, Florian Berger, Hao Jia

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(41), P. 14615 - 14619

Published: Aug. 7, 2019

Abstract Incorporation of the CF 3 group into arenes has found increasing importance in drug discovery. Herein, we report first photoredox‐catalyzed cross‐coupling aryl thianthrenium salts with a copper‐based trifluoromethyl reagent, which enables site‐selective late‐stage trifluoromethylation arenes. The reaction proceeds broad functional tolerance, even for complex small molecules on gram scale. method was further extended to produce pentafluoroethylated derivatives.

Language: Английский

Citations

219

Upcycling to Sustainably Reuse Plastics DOI
Xin Zhao, Bhanupriya Boruah,

Kek Foo Chin

et al.

Advanced Materials, Journal Year: 2021, Volume and Issue: 34(25)

Published: July 8, 2021

Plastics are now indispensable in daily lives. However, the pollution from plastics is also increasingly becoming a serious environmental issue. Recent years have seen more sustainable approaches and technologies, commonly known as upcycling, to transform into value-added materials chemical feedstocks. In this review, latest research on upcycling presented, with greater focus use of renewable energy well selective methods repurpose synthetic polymers. First, thermal briefly introduced, including redeployment for construction uses, 3D printing precursors, lightweight materials. Then, some novel strategies deconstruct condensation polymers monomers repolymerization or introduce vulnerable linkers make degradable discussed. Subsequently, review will explore breakthroughs by heterogeneous homogeneous photocatalysis, electrocatalysis, which versatile fine chemicals while simultaneously mitigating global climate change. addition, biotechnological advances discovery engineering microbes that can decompose presented. Finally, current challenges outlook future discussed stimulate cooperation field.

Language: Английский

Citations

203

Visible-Light-Mediated Regioselective Chlorosulfonylation of Alkenes and Alkynes: Introducing the Cu(II) Complex [Cu(dap)Cl2] to Photochemical ATRA Reactions DOI
Asik Hossain, Sebastian Engl, Eugen Lutsker

et al.

ACS Catalysis, Journal Year: 2018, Volume and Issue: 9(2), P. 1103 - 1109

Published: Dec. 21, 2018

A visible-light-mediated photocatalyzed protocol utilizing copper–phenanthroline-based catalysts has been developed that can convert a large number of olefins into their chlorosulfonylated products. Besides the Cu(I) complex [Cu(dap)2]Cl, now well-established in photo-ATRA processes, corresponding Cu(II) [Cu(dap)Cl2] proved to be often even more efficient title reaction, being advantageous from an economic point view but also opening up new avenues for photoredox catalysis. Moreover, copper complexes outperformed commonly used ruthenium, iridium, or organic dye based photocatalysts, owing ability stabilize interact with transient radicals by inner sphere mechanisms. The use stoichiometric Na2CO3 combination photocatalysts was found essential unactivated desired products, contrast activated which no additive required. As suggested appropriate control experiments, role is attributed prevention poisoning catalyst.

Language: Английский

Citations

194

Cross-Electrophile Coupling of Unactivated Alkyl Chlorides DOI
Holt A. Sakai, Wei Liu, Chi “Chip” Le

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(27), P. 11691 - 11697

Published: June 20, 2020

Alkyl chlorides are bench-stable chemical feedstocks that remain among the most underutilized electrophile classes in transition metal catalysis. Overcoming intrinsic limitations of C(sp3)–Cl bond activation, we report development a novel organosilane reagent can participate chlorine atom abstraction under mild photocatalytic conditions. In particular, describe application this mechanism to dual nickel/photoredox catalytic protocol enables first cross-electrophile coupling unactivated alkyl and aryl chlorides. Employing these low-toxicity, abundant, commercially available organochloride building blocks, methodology allows access broad array highly functionalized C(sp2)–C(sp3) coupled adducts, including numerous drug analogues.

Language: Английский

Citations

192

Metallaphotoredox-Catalyzed Cross-Electrophile Csp3–Csp3 Coupling of Aliphatic Bromides DOI

Russell T. Smith,

Xiaheng Zhang, Juan A. Rincón

et al.

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(50), P. 17433 - 17438

Published: Dec. 5, 2018

A strategy for the installation of small alkyl fragments onto pharmaceutically relevant aliphatic structures has been established via metallaphotoredox catalysis. Herein, we report that tris(trimethylsilyl)silanol can be employed as an effective halogen abstraction reagent that, in combination with photoredox and nickel catalysis, allows a generic approach to Csp3–Csp3 cross-electrophile coupling. In this study, demonstrate variety drug-like groups successfully coupled number commercially available electrophiles, including methyl tosylate strained cyclic bromides. Moreover, union two secondary carbon centers, long-standing challenge organic molecule construction, accomplished wide array structural formats. Last, technology selectively merged Csp2–Csp3 aryl–alkyl couplings build systems highly modular fashion.

Language: Английский

Citations

185