Ni-Catalyzed Regioselective Alkylarylation of Unactivated Alkenes in Amines Enabled by Cooperative Ligand Effects of Nitriles and Electron-Deficient Alkenes

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(2), P. 1667 - 1676

Published: Jan. 7, 2025

We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides alkylzinc reagents. The reaction is enabled by amine coordination can use all primary, secondary, tertiary amines. constructs two new C(sp3)-C(sp3) C(sp3)-C(sp2) bonds produces δ- ε-arylamines C(sp3)-branching at the γ- δ-positions. A variety heteroaryl iodides both primary secondary reagents be used as coupling carbon sources. Mechanistic studies suggest that cooperative effect organic nitriles electron-deficient (EDAs) ligands.

Language: Английский

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Cobalt-catalyzed conformationally restricted alkylarylation enables divergent access to Csp³-rich N-heterocycles

Chemical Science, Journal Year: 2024, Volume and Issue: 15(39), P. 16250 - 16258

Published: Jan. 1, 2024

Due to the intrinsic spatial orientation and structural novelty, Csp3-rich N-heterocycles have been recognized as increasingly sought-after scaffolds compared aromatic ring-based moieties, which generated considerable recent attention in drug discovery. Hence, we disclose a modular cobalt-catalyzed conformationally restricted alkylarylation strategy for divergent access N-hetero(spiro)cycles. Herein, multiple effects, including radical rebound conformational restriction, play critical roles stabilization of stereospecific alkyl-cobalt-aryl intermediate. Under simple mild reaction conditions, cobalt catalyst combines range polyfunctionalized cyclenyl bromides organozinc pivalates rapidly reliably forge architecturally complex N-hetero(spiro)cycles (>70 examples, >20 : 1 dr), but not limited [5,5]-, [5,6]-, [5,7]-, [5,12]-bicycles, tri- tetracyclic N-heterocycles, well various novel N-heterospirocyclic one synthetic operation. Preliminary kinetic investigations suggested that final reductive elimination might be rate-determining step. Moreover, ample substrate scope, good functional group compatibility facile derivatizations pharmaceutically active molecules show potential applications this technology organic syntheses discoveries medicinal chemistry.

Language: Английский

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A General Amino–(Hetero)arylation of Simple Olefins with (Hetero)aryl Sulfonamides Enabled by an N-Triazinyl Group

ACS Catalysis, Journal Year: 2025, Volume and Issue: 15(3), P. 2139 - 2149

Published: Jan. 22, 2025

(Hetero)arylethylamines are privileged substructures in pharmaceuticals, agrochemicals, and other bioactive compounds. In principle, the amino–(hetero)arylation of olefins represents an ideal strategy for rapid preparation these pharmacophores, which could accelerate discovery valuable new products. Established methods, however, do not accommodate several important classes (hetero)aromatic structures, precludes access to appreciable range molecular architectures. To address limitations, we have developed a radical-mediated reaction that adds amino (hetero)aryl groups from simple stable sulfonamide across alkene. The identification readily available triazine as original N-protecting group was critical development this transformation. features good regio- stereoselectivity succeeds with medicinally unproductive alternate protocols. Lastly, highlighted advances by synthesizing TMP269, class IIa histone deacetylase inhibitor would otherwise be challenging prepare olefin amino–arylation.

Language: Английский

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Alkylarylation of alkenes with arylsulfonylacetate as bifunctional reagent via photoredox radical addition/smiles rearrangement cascade

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110253 - 110253

Published: July 1, 2024

Language: Английский

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Vicinal Difunctionalization of Unactivated Alkenes Through Radical Addition/Remote (Hetero)Aryl Migration Cascade

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(43)

Published: Sept. 9, 2024

Abstract Alkenes are ubiquitous in natural and synthetic molecules constitute versatile building blocks. Remarkably, their radical 1,2‐difunctionalization offers a valuable tool for rapidly accessing multifunctional compounds through step atom‐ economy process. More particularly, the addition of (hetero)aromatic groups onto alkenes is particular appeal given numerous applications aromatic various fields. However, such process becomes difficult when attempted on simple non‐conjugated aliphatic (unactivated alkenes). In this context, (hetero)arylation unactivated functionalization followed by remote (hetero)aryl migration has recently emerged as powerful opportunity to address lack reactivity π systems. The advances chemistry have led flood methods trigger carbon‐ or heteroatom‐centered radical/(hetero)aryl sequence. Interestingly, ring can take place from atoms. This feature spurred design several substrates allowing occur. review intends provide an overview contributions according type that been employed. reaction scope, limitations mechanistic aspect will be discussed with aim stimulating efforts research area.

Language: Английский

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Photoinduced B–H Arylation of N-Heterocyclic Carbene Boranes with Sulfonyl(hetero)arenes

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 5, 2024

Arylborane complexes ligated by N-heterocyclic carbenes (NHCs) can be synthesized photoirradiation of a mixture NHC-boranes and sulfonyl(hetero)arenes. The reaction occurs under mild convenient conditions without any photocatalyst, which are realized radical chain mechanism involving NHC-boryl radicals sulfonyl radicals. This offered the opportunity to reveal photophysical property 2-borylnaphtho[1,2-

Language: Английский

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Alkylcyanation of Unactivated Alkenes with Protic C(sp3)‐H Feedstocks via Radical‐Initiated Intramolecular Cyano Group Migration Enabled by Photoredox/Brønsted Base Dual Catalysis

ChemPhotoChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Abstract Cyanofunctionalization of alkenes via radical‐initiated cyano migration was a straightforward pathway to access alkyl nitriles. Herein, By the synergistic merger photoredox catalysis and Brønsted base catalysis, mild protocol alkylcyanation unactivated with protic C(sp 3 )−H feedstocks intramolecular 1,4‐cyano group reported. This method enabled in an atom‐, step‐economy manner, delivering series γ‐cyanoester derivatives moderate excellent yields.

Language: Английский

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Aminoarylation of Alkynes using Diarylanilines

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(49), P. 6296 - 6299

Published: Jan. 1, 2024

Intermolecular aminoarylation of alkynes is described,

Language: Английский

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