Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides: regiochemistry, indigoid formation and methyl migration-aromatization

Geden, Joanna V.; Clark, Andrew J.; Coles, Stuart R.; Guy, Collette S.; Ghelfi, Franco; Thom, Stephen

doi:10.1016/j.tetlet.2016.06.009

Cited by 6 publications

(4 citation statements)

References 47 publications

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“…[1][2][3] Being atomically economic and versatile, this type of reaction provides a variety of functionalized compounds that can be used for further synthesis of chemical feedstocks, advanced materials, and pharmaceuticals. [4][5][6] To date, several metal complexes based on iron, copper, ruthenium, osmium, niobium, and molybdenum have been recognized as promoters for ATRA reactions under thermal conditions. [7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] However, the alkene substrate scope in these processes is rather limited and especially unsuccessful for active alkenes that are prone to competitive polymerization.…”

Section: Introductionmentioning

confidence: 99%

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Copper(ii) complexes of quinoline-based ligands for efficient photoredox catalysis of atom transfer radical addition (ATRA) reaction

et al. 2022

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Section: Introductionmentioning

confidence: 99%

“…1–3 Being atomically economic and versatile, this type of reaction provides a variety of functionalized compounds that can be used for further synthesis of chemical feedstocks, advanced materials, and pharmaceuticals. 4–6…”

Section: Introductionmentioning

confidence: 99%

Copper(ii) complexes of quinoline-based ligands for efficient photoredox catalysis of atom transfer radical addition (ATRA) reaction

et al. 2022

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“…When using the CuCl:TPMA system for the radical cyclization of 1-substituted enamides, the substituent was able to stabilize the cyclized radical to force the 5-endo process. 31 Thus, from enamide 38a, the hydroxylated products 39 were isolated, which probably arose from an oxidation of a radical intermediate by CuCl 2 :TPMA, giving an acyl iminium that reacted with water upon work-up. The related compound 38b followed a different pathway, providing the indigoid derivative 40 of unknown configuration in low yield (Scheme 22).…”

Section: Scheme 21 Synthesis Of δ-Lactams Using Multidentate Amine LImentioning

confidence: 99%

“…From trienamide 44b, using the catalytic system CuCl:TPMA, only the 4-exo cyclization compound 45b was isolated in poor yield. 31…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Radical Cyclization of Trichloroacetamides: Synthesis of Lactams

Coussanes¹,

Vilà²,

Diaba³

et al. 2017

Synthesis

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Trichloroacetamides can act as radical precursors to synthesize nitrogen-containing heterocycles in a variety of processes, mainly involving atom transfer radical cyclizations (ATRC), mediated by Cu(I) or Ru(II) catalysts, and the hydride reductive method, employing either Bu 3 SnH or (Me 3 Si) 3 SiH, or recently NaBH 3 CN. Additionally, amine-mediated single-electron transfer cyclizations, as well as radical processes promoted by Ni, Fe, Mn, Ti, and Ag, have been developed. 1 Introduction 2 Atom Transfer Radical Cyclizations (ATRC) 2.

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β,β,β‐Trichloroethyl‐NH‐Enamine as Viable System for 5‐Endo‐trig Radical Cyclization via Multifaceted Cu^I−Cu^II Redox Catalysis: Single Step Synthesis of Multi‐Functionalized NH‐Pyrroles

2019

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Here we report a mild and regioselective copper-catalyzed direct synthesis of multi-substituted and functionalized NH-pyrroles in high yields from diverse β,β,β-trichloroethyl-NH-enamines via a novel 5-endo-trig radical cyclization mode, previously known to be unviable in the enamine system. An approach to transform a geometrically 'disfavored to favored' 5-endo-trig radical cyclization mode in NH-enamine systems via multifaceted Cu I À Cu II redox catalysis generating radicals, preventing dehalogenative reduction of radical precursors and dehydrohalogenating the 5-endo-trig cyclized products have been demonstrated experimentally. With wider substrate scope, this method incorporates halo-, NH-and carbonyl functionalities besides alkyl, aryl and heteroaryl substituents in the pyrrole unit easily. These difficult to prepare 3-halo-NH-pyrroles are potential sources for natural products, agrochemicals, pharmaceuticals and organometallic chemistry. Scheme 1. a) Viable 5-endo-trig radical cyclizations in N-substituted enamide, b) unviable 5-endo-trig radical cyclizations in Nsubstituted enamine and c) transformation of unviable to viable mode in present work. UPDATES asc.wiley-vch.de Scheme 2. Synthesis of 3-chloro-NH-pyrroles 21 by Cu(I)/PMDETA-catalyzed 5-endo-trig radical cyclization-aromatization of NHenamines 20.Scheme 4. Study of the conformational role of substituents and functionalities of NH-enamines in the 5-endo-trig radical cyclization process.

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Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides: regiochemistry, indigoid formation and methyl migration-aromatization

Cited by 6 publications

References 47 publications

Copper(ii) complexes of quinoline-based ligands for efficient photoredox catalysis of atom transfer radical addition (ATRA) reaction

Copper(ii) complexes of quinoline-based ligands for efficient photoredox catalysis of atom transfer radical addition (ATRA) reaction

Radical Cyclization of Trichloroacetamides: Synthesis of Lactams

β,β,β‐Trichloroethyl‐NH‐Enamine as Viable System for 5‐Endo‐trig Radical Cyclization via Multifaceted Cu^I−Cu^II Redox Catalysis: Single Step Synthesis of Multi‐Functionalized NH‐Pyrroles

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Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides: regiochemistry, indigoid formation and methyl migration-aromatization

Cited by 6 publications

References 47 publications

Copper(ii) complexes of quinoline-based ligands for efficient photoredox catalysis of atom transfer radical addition (ATRA) reaction

Copper(ii) complexes of quinoline-based ligands for efficient photoredox catalysis of atom transfer radical addition (ATRA) reaction

Radical Cyclization of Trichloroacetamides: Synthesis of Lactams

β,β,β‐Trichloroethyl‐NH‐Enamine as Viable System for 5‐Endo‐trig Radical Cyclization via Multifaceted CuI−CuII Redox Catalysis: Single Step Synthesis of Multi‐Functionalized NH‐Pyrroles

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β,β,β‐Trichloroethyl‐NH‐Enamine as Viable System for 5‐Endo‐trig Radical Cyclization via Multifaceted Cu^I−Cu^II Redox Catalysis: Single Step Synthesis of Multi‐Functionalized NH‐Pyrroles