Nickel-Catalyzed Dicarbofunctionalization of Alkenes

ACS Catalysis, Год журнала: 2020, Номер 10(15), С. 8542 - 8556

Опубликована: Июль 2, 2020

1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available with electrophiles and/or nucleophiles. Nickel complexes serve effective catalysts owing to their tendency undergo facile oxidative addition and slow β-hydride elimination, capability access both two-electron radical pathways. Two-component alkene functionalization reactions have achieved high chemo-, regio-, stereoselectivities tethering one the partners substrate. Three-component reactions, however, often incorporate directing groups control selectivity. Only a few examples directing-group-free difunctionalizations unactivated been reported. Therefore, great opportunities exist development three-component difunctionalization broad substrate scopes tunable stereoselectivities.

Язык: Английский

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Nitrogen-Centered Radicals in Functionalization of sp² Systems: Generation, Reactivity, and Applications in Synthesis

Chemical Reviews, Год журнала: 2022, Номер 122(9), С. 8181 - 8260

Опубликована: Март 14, 2022

The chemistry of nitrogen-centered radicals (NCRs) has plentiful applications in organic synthesis, and they continue to expand as our understanding these reactive species increases. utility intermediates is demonstrated the recent advances C–H amination (di)amination alkenes. Synthesis previously challenging structures can be achieved by efficient functionalization sp2 moieties without prefunctionalization, allowing for faster more streamlined synthesis. This Review addresses generation, reactivity, application NCRs, including, but not limited to, iminyl, aminyl, amidyl, aminium species. Contributions from early discovery up most examples have been highlighted, covering radical initiation, thermolysis, photolysis, and, recently, photoredox catalysis. Radical-mediated intermolecular (hetero)arenes occur with a variety complex amine precursors, generating aniline derivatives, an important class drug development. Functionalization olefins achievable high anti-Markovnikov regioselectivity allows access difunctionalized when intermediate carbon are trapped. Additionally, reactivity NCRs harnessed rapid construction N-heterocycles such pyrrolidines, phenanthridines, quinoxalines, quinazolinones.

Язык: Английский

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Cooperative NHC and Photoredox Catalysis for the Synthesis of β‐Trifluoromethylated Alkyl Aryl Ketones

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(45), С. 19956 - 19960

Опубликована: Июль 23, 2020

Despite the great potential of radical chemistry in organic synthesis, N-heterocyclic carbene (NHC)-catalyzed reactions involving intermediates are not well explored. This communication reports three-component coupling aroyl fluorides, styrenes and Langlois reagent (CF3 SO2 Na) to give various β-trifluoromethylated alkyl aryl ketones with good functional group tolerance moderate high yields by cooperative photoredox/NHC catalysis. The alkene acyltrifluoromethylation proceeds via radical/radical cross ketyl radicals benzylic C-radicals. generated SET reduction situ formed acylazolium ions whereas derive from trifluoromethyl addition onto styrenes.

Язык: Английский

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Radical NHC Catalysis

ACS Catalysis, Год журнала: 2022, Номер 12(19), С. 11984 - 11999

Опубликована: Сен. 19, 2022

Radical/radical cross-coupling reactions represent an efficient and straightforward approach for the construction of chemical bonds accordingly have drawn increasing attention over past decades. In order to achieve synthetically useful transformations, a persistent radical should be coupled with transient in accordance effect (PRE). However, known radicals outnumber by far types free radicals, which limits widespread application PRE, until today. Thus, development between has been focus, meanwhile transition-metal catalysis successfully implemented artificially prolong lifetimes, allowing their utilization formal radical/radical cross-couplings. Complementary research field recently uncovered that organocatalytically generated NHC-derived ketyl are type catalytically radicals. NHC-catalyzed transformations aldehydes carboxylic acid derivatives enabled disclosure ever-increasing number interesting reactions, different from traditional ionic processes, offering otherwise inaccessible activation modes. These discoveries opened door NHC organocatalysis manipulation reactions. Due its obvious potential synthetic organic chemistry, it is timely provide perspective on this emerging field.

Язык: Английский

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Recent advances in visible-light photoredox-catalyzed nitrogen radical cyclization

Green Synthesis and Catalysis, Год журнала: 2020, Номер 1(1), С. 42 - 51

Опубликована: Июнь 1, 2020

Visible-light photoredox catalysis is a powerful and attractive strategy for organic molecule activation new reaction design owing to its environmental-friendly characteristics unique catalytic mechanisms, has found wide applications in synthesis. This enables controllable generation of diverse nitrogen-centered radicals (NCRs) under mild conditions, providing access construction nitrogen-containing compounds. In this review, we critically illustrate the recent advances field visible-light photoredox-catalyzed cyclization radicals, based on different radical precursors modes. Wherever possible, particular emphasis also put working models synthetic applications.

Язык: Английский

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Bifunctional reagents in organic synthesis

Nature Reviews Chemistry, Год журнала: 2021, Номер 5(5), С. 301 - 321

Опубликована: Апрель 12, 2021

Язык: Английский

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Recent advance in the C–F bond functionalization of trifluoromethyl-containing compounds

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(14), С. 3915 - 3942

Опубликована: Янв. 1, 2021

The C–F bond is the strongest single in organic compounds.

Язык: Английский

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Electro-/photocatalytic alkene-derived radical cation chemistry: recent advances in synthetic applications

Chemical Society Reviews, Год журнала: 2022, Номер 51(16), С. 7206 - 7237

Опубликована: Янв. 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.

Язык: Английский

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Recent developments in the difunctionalization of alkenes with C–N bond formation

Organic Chemistry Frontiers, Год журнала: 2021, Номер 8(18), С. 5206 - 5228

Опубликована: Янв. 1, 2021

Various alkene difunctionalization reactions involving nitridization, diamination, azidation, oxyamination, carboamination, aminohalogenation, and nitration are introduced in this review.

Язык: Английский

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Ni-Catalyzed Ligand-Controlled Regiodivergent Reductive Dicarbofunctionalization of Alkenes

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(27), С. 10282 - 10291

Опубликована: Июнь 24, 2021

Transition-metal-catalyzed dicarbofunctionalization of alkenes involving intramolecular Heck cyclization followed by intermolecular cross-coupling has emerged as a powerful engine for building heterocycles with sterically congested quaternary carbon centers. However, only exo-cyclization/cross-coupling products can be obtained; endo-selective cyclization/cross-coupling not been reported yet and still poses formidable challenge. We herein report the first example catalyst-controlled regiodivergent synthesis five- six-membered benzo-fused lactams bearing all-carbon Using chiral Pyrox- or Phox-type bidentate ligand, 5-exo cyclization/cross-couplings proceed favorably to produce indole-2-ones in good yields excellent regioselectivity enantioselectivities (up 98% ee). When C6-carboxylic acid-modified 2,2′-bipyridine was used 3,4-dihydroquinolin-2-ones were obtained through 6-endo-selective processes. This transformation is modular tolerant variety functional groups. The ligand rather than substrate structures precisely dictates pattern. Moreover, synthetic value this protocol demonstrated preparation biologically relevant molecules structural scaffolds.

Язык: Английский

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