Synthesis of Unprotected β‐Arylethylamines by Iron(II)‐Catalyzed 1,2‐Aminoarylation of Alkenes in Hexafluoroisopropanol DOI Creative Commons
Valentyn Pozhydaiev, Marie Vayer, Claire Fave

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(9)

Published: Dec. 21, 2022

β-Arylethylamines are prevalent structural motifs in molecules exhibiting biological activity. Here we report a sequential one-pot protocol for the 1,2-aminoarylation of alkenes with hydroxylammonium triflate salts and (hetero)arenes. Unlike existing methods, this reaction provides direct entry to unprotected β-arylethylamines remarkable functional group tolerance, allowing key drug-oriented groups be installed two-step process. The use hexafluoroisopropanol as solvent combination an iron(II) catalyst proved essential reaching high-value nitrogen-containing molecules.

Language: Английский

Energy transfer-enabled unsymmetrical diamination using bifunctional nitrogen-radical precursors DOI
Guangying Tan, Mowpriya Das,

Roman Kleinmans

et al.

Nature Catalysis, Journal Year: 2022, Volume and Issue: 5(12), P. 1120 - 1130

Published: Dec. 8, 2022

Language: Английский

Citations

82
Photoinduced Copper-Catalyzed Late-Stage Azidoarylation of Alkenes via Arylthianthrenium Salts DOI Creative Commons
Yuan Cai, Sagnik Chatterjee, Tobias Ritter

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(25), P. 13542 - 13548

Published: June 12, 2023

The arylethylamine pharmacophore is conserved across a range of biologically active natural products and pharmaceuticals, particularly in molecules that act on the central nervous system. Herein, we present photoinduced copper-catalyzed azidoarylation alkenes at late stage with arylthianthrenium salts, allowing access to highly functionalized acyclic (hetero)arylethylamine scaffolds are otherwise difficult access. A mechanistic study consistent rac-BINAP-CuI-azide (2) as photoactive catalytic species. We show utility new method by expedient synthesis racemic melphalan four steps through C-H functionalization.

Language: Английский

Citations

79
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

64
A general alkene aminoarylation enabled by N-centred radical reactivity of sulfinamides DOI
Efrey A. Noten, Cody Ng, Robert M. Wolesensky

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 599 - 606

Published: Jan. 16, 2024

Language: Английский

Citations

35
Chiral arylsulfinylamides as reagents for visible light-mediated asymmetric alkene aminoarylations DOI Creative Commons
Cédric Hervieu, Mariia S. Kirillova, Yawen Hu

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(4), P. 607 - 614

Published: Jan. 16, 2024

Abstract Two- or one-electron-mediated difunctionalizations of internal alkenes represent straightforward approaches to assemble molecular complexity by the simultaneous formation two contiguous C sp 3 stereocentres. Although racemic versions have been extensively explored, asymmetric variants, especially those involving open-shell C-centred radical species, are much more limited both in number and scope. Here we describe enantioenriched arylsulfinylamides as all-in-one reagents for efficient asymmetric, intermolecular aminoarylation alkenes. Under mild photoredox conditions, nitrogen addition arylsulfinylamide onto double bond, followed 1,4-translocation aromatic ring, produce, a single operation, corresponding adducts enantiomerically enriched form. The sulfinyl group acts here traceless chiral auxiliary, it is eliminated situ under reaction conditions. Optically pure β,β-diarylethylamines, aryl-α,β-ethylenediamines α-aryl-β-aminoalcohols, prominent motifs pharmaceuticals, bioactive natural products ligands transition metals, thereby accessible with excellent levels regio-, relative absolute stereocontrol.

Language: Английский

Citations

34
Aminoalkylation of Alkenes Enabled by Triple Radical Sorting DOI
William L. Lyon, Johnny Wang, Jesús Alcázar

et al.

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

Published: Jan. 9, 2025

The direct synthesis of C(sp3)-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there strong impetus to develop new methods by which access sp3-rich from commercial feedstocks, such as alkenes. Herein, we report three-component aminoalkylation reaction utilizes the principles triple radical sorting regioselectively add N-centered and C-centered radicals across This process relies upon photoredox catalysis transform alkyl bromides reductively activated precursors into high-energy species redox-neutral fashion. A broad scope coupling partners demonstrated, multiple applications, including facile syntheses pharmacophoric substituted N-heterocycles.

Language: Английский

Citations

3
Regiodivergent sulfonylarylation of 1,3-enynes via nickel/photoredox dual catalysis DOI Creative Commons
Ya Chen, Kun Zhu, Qingqin Huang

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(40), P. 13564 - 13571

Published: Jan. 1, 2021

Catalytic difunctionalization of 1,3-enynes represents an efficient and versatile approach to rapidly assemble multifunctional propargylic compounds, allenes 1,3-dienes. Controlling selectivity in such addition reactions has been a long-standing challenging task due multiple reactive centers resulting from the conjugated structure 1,3-enynes. Herein, we present straightforward method for regiodivergent sulfonylarylation via dual nickel photoredox catalysis. Hinging on nature 1,3-enynes, diverse reaction pathways are feasible: synthesis α-allenyl sulfones 1,4-sulfonylarylation, or preparation (E)-1,3-dienyl with high chemo-, regio- stereoselectivity through 3,4-sulfonylarylation. Notably, this is first example that catalysis merged achieve

Language: Английский

Citations

76
Three‐Component Aminoarylation of Electron‐Rich Alkenes by Merging Photoredox with Nickel Catalysis DOI Creative Commons
Heng Jiang, Xiaoye Yu, Constantin G. Daniliuc

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(26), P. 14399 - 14404

Published: April 19, 2021

A three-component 1,2-aminoarylation of vinyl ethers, enamides, ene-carbamates and thioethers by synergistic photoredox nickel catalysis is reported. 2,2,2-Trifluoroethoxy carbonyl protected α-amino-oxy acids are used as amidyl radical precursors. anti-Markovnikov addition the to alkene Ni-mediated radical/transition metal cross over lead corresponding product. The cascade, which can be conducted under practical mild conditions, features high functional group tolerance broad substrate scope. Stereoselective achieved using a L-(+)-lactic acid derived ether substrate, offering novel route for preparation enantiopure α-arylated β-amino alcohols. In addition, 1,2-aminoacylation ethers an acyl succinimide electrophile coupling.

Language: Английский

Citations

61
Three-component carboacylation of alkenes via cooperative nickelaphotoredox catalysis DOI Creative Commons
Dingyi Wang, Lutz Ackermann

Chemical Science, Journal Year: 2022, Volume and Issue: 13(24), P. 7256 - 7263

Published: Jan. 1, 2022

Various commercially available acyl chlorides, aldehydes, and alkanes were exploited for versatile three-component 1,2-carboacylations of alkenes to forge two vicinal C-C bonds through the cooperative action nickel sodium decatungstate catalysis. A wealth ketones with high levels structural complexity was rapidly obtained via direct functionalization C(sp2)/C(sp3)-H in a modular manner. Furthermore, regioselective late-stage modification natural products showcased practical utility strategy, generally featuring resource economy ample substrate scope.

Language: Английский

Citations

51
Modular Synthesis of Multifunctionalized CF3-Allenes through Selective Activation of Saturated Hydrocarbons DOI
Wenfeng Liu,

Chuhan Liu,

Minyan Wang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(16), P. 10207 - 10221

Published: Aug. 5, 2022

Catalytic 1,4-dicarbofunctionalization of 1,3-enynes is a powerful strategy for the synthesis polysubstituted allenes. Despite impressive progress, such still restricted to use alkyl-metallic reagents or pre-activated radical precursors, thus limiting its functional group compatibility and atom economy. Herein, we report that through combination decatungstate photo-hydrogen transfer nickel catalysis, three-component 2-trifluoromethyl-1,3-enynes achieved. This allows modular tetrasubstituted CF3-allenes under exceptionally mild conditions. A variety electrophiles as aryl bromides, alkenyl acyl chlorides, alkynyl bromides were successfully employed traps lead desired products. Another significant advantage most abundant hydrocarbons are used feedstocks, wide range synthetically versatile groups complex drug-like structures can be easily incorporated. Based on experimental density theories, possible catalytic cycle involving 1,3-nickel rearrangement proposed.

Language: Английский

Citations

49