A unified strategy involving visible-light-induced iminyl-radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac-[Ir(ppy)3 ] as a photoredox catalyst, oximes were converted by 1 e(-) reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give N-containing arenes. These reactions proceeded with broad range substrates at room temperature in high...

Bring to light: The first visible-light-promoted somophilic isocyanide insertion occurs using an iridium photocatalyst. This efficient synthetic approach provides a rapid entry 6-alkylated phenanthridine derivatives (see scheme). reactions proceed at room temperature in good excellent yields with broad substrate scope and under environmentally friendly conditions. As service our authors readers, this journal supporting information supplied by the authors. Such materials are peer reviewed may...

A practical and unified strategy has been described for the preparation of mono- difluoromethylated phenanthridine derivatives using a visible-light-promoted alkylation decarboxylation sequence from biphenyl isocyanides with ethyl bromofluoroacetate (EBFA) or bromodifluoroacetate (EBDFA). These reactions could be carried out at room temperature in good to excellent chemical yields. Both stepwise one-pot procedures have developed, which makes this more attractive.

Highly regio- and enantioselective allylic alkylation has been achieved enabled by the merger of photoredox palladium catalysis. In this dual catalytic process, alkyl radicals generated from 4-alkyl-1,4-dihydropyridines act as coupling partners π-allyl complexes. The generality method illustrated through reaction a variety allyl esters with 4-alkyl-1,4-dihydropyridines. This mechanistically novel strategy expands scope traditional Pd-catalyzed asymmetric serves its alternative potential complement.

A visible-light-promoted C(sp(3))-H amidation and chlorination of N-chlorosulfonamides (NCSs) is reported. This remote functionalization can be achieved in weak basic solution at room temperature with as little 0.1 mol % a photocatalyst. variety nitrogen-containing heterocycles (up to 94% yield) chlorides 93% are prepared from NCSs. Late-stage complex biologically important (-)-cis-myrtanylamine (+)-dehydroabietylamine derivatives also excellent yields regioselectivity.

A halogen-bond-promoted double radical isocyanide insertion with perfluoroalkyl iodides is reported. With as halogen-bond donors and organic bases acceptors, fluoroalkyl radicals can be generated by a visible-light-induced single electron transfer (SET) process. The are trapped o-diisocyanoarenes to give quinoxaline derivatives. This mechanistically novel strategy allows the construction of 2-fluoroalkylated 3-iodoquinoxalines in high yields under visible-light irradiation at room temperature.

Organocatalysis: A highly effective catalytic procedure for the Michael addition of aldehydes to nitroalkenes is achieved by combining excellent asymmetric induction ability o-TMS-protected diphenylprolinol compounds, quick formation enamines in presence benzoic acid, and concentrated organic phase water (see scheme; TMS=trimethylsilyl). Supporting information this article available on WWW under http://www.wiley-vch.de/contents/jc_2002/2008/z704161_s.pdf or from author. Please note: The...

CuI/bis(oxazoline)-catalyzed addition of propiolates and terminal ynones to 1-acylpyridinium salt (generated in situ from reaction pyridine methyl chloroformate) affords highly functionalized dihydropyridines with excellent enantioselectivity. It is found that the carbonyl group adjacent alkyne moiety essential for enantioselectivity addition. Short synthesis indolizidines 167B 223AB achieved by employing two products.

Abstract Direct CH functionalization of various enamides and enecarbamates was realized through visible‐light photoredox catalyzed reactions. Under the optimized conditions using [Ir(ppy) 2 (dtbbpy)PF 6 ] as photocatalyst in combination with Na HPO 4 , such N ‐vinylpyrrolidinone could be easily functionalized by irradiation reaction mixture overnight acetonitrile visible light. The scope respect to enamide enecarbamate substrates diethyl 2‐bromomalonate for alkylation explored, followed an...

A room temperature redox neutral direct C–H amidation of heteroarenes has been achieved. Hydroxylamine derivatives, which are easily accessed, have employed as tunable nitrogen sources. These reactions were enabled by a visible-light-promoted single-electron transfer pathway without directing group. variety heteroarenes, such indoles, pyrroles, and furans, could go through this with high yields (up to 98%). highly regioselective, all the products isolated single regioisomer.

Hey Mickey, you're so fine! Organocatalytic Michael additions of aldehydes with protected 2-amino-1-nitroethene could go through three different transition-states to afford adducts usual and unusual stereochemistry, thereby providing a facile entry Tamiflu (see scheme) substituted 3-aminopyrrolidines. TMS=trimethylsilyl, Ac=acetyl.

A one-pot synthesis of phenanthridines and quinolines from commercially available or easily prepared aldehydes has been reported. O-(4-Cyanobenzoyl)hydroxylamine was utilized as the nitrogen source to generate O-acyl oximes in situ with catalyzed by Brønsted acid. O-Acyl were then subjected visible light photoredox cyclization via iminyl radicals furnish aza-arenes. variety have assisted acid photocatalyst under at room temperature satisfactory yields.

An electron-donor–acceptor (EDA) complex between Togni's reagent and a tertiary amine has been introduced. The existence of this EDA was supported by NMR titration experiments. hydrotrifluoromethylation unactivated aliphatic alkenes alkynes enabled also developed. This protocol is operationally simple promoted amine.

A unified strategy for intermolecular remote C(sp3)–H and C–C vinylation of O-acyl oximes with vinyl boronic acids has been achieved. This is enabled by photoreductive generation iminyl radicals from under irradiation visible light. The translocated carbon-centered radicals, which are generated the through 1,5-hydrogen atom transfer or cleavage, can be vinylated acids. opens up a new approach to functionalization via cleavage provides an efficient versatile solution synthesis γ-vinylation...

Abstract A mild, practical method to prepare α‐sulfonyl and α‐trifluoromethyl ketones from readily available enol acetates sulfonyl chlorides has been developed using visible‐light photoredox catalysis. The could be used with a wide range of chlorides, gave the desired products in satisfactory excellent yields.

Radical alkynyltrifluoromethylation of alkenes with actylenic triflones has been achieved. This radical chain reaction is initiated by a catalytic amount an electron-donor–acceptor complex composed Togni's reagent and N-methylmorpholine. transformation proceeds under exceptionally mild operationally simple conditions. A variety are compatible in this protocol including aliphatic alkenes, vinyl ethers, enecarbamates, styrenes, even acrylates, providing diverse β- trifluoromethyl alkynes good...

A novel electron-donor-acceptor (EDA) complex-mediated direct C-H trifluoromethylation of arenes with Umemoto's reagent has been developed. This transformation enabled by an unprecedented EDA complex formed and amine, which was supported experiments theoretical calculations. The radical-based methodology presented here allows to access highly-functionalized trifluoromethyl in up 81 % chemical yield.

A mechanistically new strategy has been described for the simple, practical, and environmentally friendly preparation of 6-(trifluoromethyl)phenanthridine derivatives using ionic isocyanide insertion from biphenyl Umemoto's reagent. These reactions were promoted only by inorganic base in good-to-excellent chemical yields without any external stoichiometric oxidants radical initiators.

A synthetic strategy for multi-substituted isoquinoline derivatives has been developed using visible light-promoted vinyl isocyanide insertion with diaryliodonium salts at room temperature. The methodology presented here represents the first example of synthesis via somophilic insertion.

A conceptually new strategy has been described for the mild, practical, and environmentally friendly preparation of naphthols furans using a visible-light promoted photoredox neutral approach. These reactions between accessible electron-deficient bromides commercially available alkynes could be carried out at room temperature in good-to-excellent chemical yields without any external stoichiometric oxidants.

Radical translocation processes triggered by nitrogen-centered radicals (NCRs), such as 1,5-hydrogen atom transfers (1,5-HAT), demonstrated the well-established Hofmann-Löffler-Freytag (HLF) reaction, provide an attractive approach for controllable and selective functionalization of remote inert C(sp3)-H bonds. Here we report amidyl radical-triggered site-selective heteroarylation amides under organic photoredox conditions. This provides a mild highly regioselective reaction affording...

Abstract A unified strategy involving visible‐light‐induced iminyl‐radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac ‐[Ir(ppy) 3 ] as a photoredox catalyst, oximes were converted by 1 e − reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give N‐containing arenes. These reactions proceeded with broad range substrates at room temperature in...