Substituent-Controlled Copper-Catalyzed Trifluoromethylation of 1,7-Dienes: Synthesis of Mono- and Bis-trifluoromethylated Benzoxepines.

A copper-catalyzed trifluoromethylation of benzene-linked 1,7-dienes with 1-trifluoromethyl-1,2-benziodoxole via a radical cascade cyclization process for the synthesis of mono- and bis-trifluoromethylated benzoxepines is developed. The selectivity depends on substituents on the double bond of the allyl group in 1,7-dienes. The large-scale operation and late-stage functionalization of bioactive molecules reveal the promising utility of this protocol.

Visible-Light-Induced Regioselective Cascade Radical Cyclization of α-Bromocarbonyls: Access to Benzazepine Derivatives.

Visible-light-induced regioselective cascade radical cyclization of α-bromocarbonyls for the synthesis of benzazepine derivatives is described. In the presence of fac-Ir(ppy)3 (2.0 mol %) as a photocatalyst, 2,6-lutidine as a base, and dichloromethane as a solvent, the reactions proceed smoothly to afford seven-membered rings in good yields. This protocol features a broad substrate scope, excellent functional group tolerance, and mild reaction conditions. Preliminary mechanistic studies reveal that the generation of the α-carbon radical is more prone to react with the 1,1-diphenylethylene tethered acrylamide to generate the stable seven-membered heterocycle.

NHC-Catalyzed Tandem Reaction: A Strategy for the Synthesis of 2-Pyrrolidinone-Functionalized Phenanthridines.

Herein, an N-heterocyclic carbene (NHC)-catalyzed tandem cyclization/addition/cyclization reaction of 2-isocyanobiaryls and α-bromo-N-cinnamylamides for the synthesis of 2-pyrrolidinone-functionalized phenanthridines is developed. This protocol features a radical cascade process, broad substrate scope, and good functional group compatibility under metal- and oxidant-free reaction conditions.

NHC-Catalyzed Regioselective Intramolecular Radical Cyclization Reaction for the Synthesis of Benzazepine Derivatives.

A novel and efficient strategy for the synthesis of a series of structurally interesting benzazepine derivatives via an N-heterocyclic carbene-catalyzed regioselective intramolecular radical cyclization has been developed. This protocol features good regioselectivity, good functional-group compatibility, and wide substrate scope, providing a transition-metal- and oxidant-free pathway to access the seven-membered rings under mild reaction conditions. Additionally, further transformation of benzazepines and a large-scale experiment were also conducted.

Visible-Light-Induced Difluoroalkylation of 1-(Allyloxy)-2-(1-arylvinyl)benzenes and 1-(1-Arylvinyl)-2-(vinyloxy)benzenes: Synthesis of Bis-Difluoroalkylated Benzoxepines and 2H-Chromenes.

A novel visible-light-mediated difluoroalkylation of 1-(allyloxy)-2-(1-arylvinyl)benzenes and 1-(1-arylvinyl)-2-(vinyloxy)benzenes for the synthesis of bis-difluoroalkylated benzoxepines and 2H-chromenes is developed. This method features mild reaction conditions, good regioselectivity, a wide substrate scope, good functional-group compatibility, and late-stage modification. Preliminary mechanistic studies reveal that the generation of the CF2CO2Et radical is more prone to reaction with the double bond of the aryl group.

Visible-Light-Induced Cascade Cyclization of N-Propargyl Aromatic Amines and Acyl Oxime Esters: Rapid Access to 3-Acylated Quinolines.

Visible-light-induced radical cascade acylation/cyclization/aromatization of N-propargyl aromatic amines and acyl oxime esters for the construction of 3-acylated quinolines is developed. This approach uses acyl oxime esters as the precursor of acyl radicals as well as acylation reagents, Eosin Y as the photocatalyst, and acetonitrile as the solvent, providing a convenient route toward 3-acylated quinolines via the C-C bond cleavage of acyl oxime esters.

Palladium-catalyzed radical cascade cyanoalkylsulfonylation/cyclization of 3-arylethynyl-[1,1'-biphenyl]-2-carbonitriles with cyclobutanone oxime esters and DABSO.

A palladium-catalyzed radical cascade cyanoalkylsulfonylation/cyclization of 3-arylethynyl-[1,1'-biphenyl]-2-carbonitriles with DABCO·(SO2)2 and cyclobutanone oxime esters via cleavage of a C-C single bond and insertion of SO2 was described. A series of cyanoalkylsulfone-containing cyclopenta[gh]phenanthridines were obtained in moderate-to-good yields, thus featuring mild reaction conditions, a broad substrate scope, and a high functional group tolerance.

Visible-Light-Induced Multicomponent Cascade Cycloaddition of N-Propargyl Aromatic Amines, Cyclobutanone Oxime Esters, and K2S2O5: Access to Cyanoalkylsulfonylated Quinolines.

A visible-light-induced cascade cyanoalkylsulfonylation/cyclization/aromatization of N-propargyl aromatic amines with K2S2O5 and cyclobutanone oxime esters for the construction of cyanoalkylsulfonylated quinolines is developed. This cascade transformation features mild reaction conditions, a broad substrate scope, and excellent functional group compatibility, providing a convenient route toward cyanoalkylsulfonylated quinolines via the formation of a C-C bond and two C-S bonds in one step.

Ni-Catalyzed radical cyclization of vinyl azides with cyclobutanone oxime esters to access cyanoalkyl containing quinoxalin-2(1H)-ones.

A nickel-catalyzed cascade addition/cyclization of 2-azido-N-arylacrylamides and cyclobutanone oxime esters for the construction of 3-cyanoalkylated quinoxalin-2(1H)-ones is developed. This reaction proceeds under mild conditions with good functional group tolerance and broad substrate scope. A preliminary mechanistic experiment indicated that the cyanoalkyl radical might be involved in this transformation.

TBPB-initiated cascade cyclization of 3-arylethynyl-[1,1'-biphenyl]-2-carbonitriles with sulfinic acids: access to sulfone-containing cyclopenta[gh]phenanthridines.

A novel TBPB-initiated cascade cyclization of 3-arylethynyl-[1,1'-biphenyl]-2-carbonitriles with sulfinic acids via C-S, C-C and C-N bond formation for the synthesis of 3-sulfonated cyclopenta[gh]phenanthridines under metal-free conditions has been developed. This protocol features mild conditions, good functional group tolerance and a broad substrate scope. By using this protocol, a variety of potentially bioactive 3-sulfonated cyclopenta[gh]phenanthridines were facilely synthesized via direct annulation.

Synergistic Photoredox Catalysis and Organocatalysis for Inverse Hydroboration of Imines.

The first catalytic inverse hydroboration of imines with N-heterocyclic carbene (NHC) boranes has been realized by means of cooperative organocatalysis and photocatalysis. This catalytic combination provides a promising platform for promoting NHC-boryl radical chemistry under sustainable and radical-initiator-free conditions. The highly important functional-group compatibility and possible application in late-stage hydroborations represent an important step forward to an enhanced α-amino organoboron library.

Harnessing sunlight without a photosensitizer for highly efficient consecutive [3+2]/[4+2] annulation to synthesize fused benzobicyclic skeletons.

A photosensitizer-free, highly efficient sunlight-promoted tandem [3+2]/[4+2] annulation of unsaturated α-bromocarbonyls with o-alkynylanilines was developed, and allowed for convenient synthesis of fused benzobicyclic skeletons. The reaction was clean and practical in mild conditions and showed excellent functional group compatibility.

[3+2] Cycloaddition of azide with aldehyde hydrazone through an aminyl radical-polar crossover strategy.

A novel approach to obtain functionalized tetrazoles by a [3+2] cycloaddition of azide with aldehyde hydrazone is reported. This reaction features a broad substrate scope and mild reaction conditions through an aminyl radical-polar crossover strategy.

Synthesis of cyclohexylidenehydrazine-fused polycyclics via a photocatalytic radical cascade reaction of 2-ethynylaldehyde hydrazones.

A general and efficient visible-light photoredox-catalyzed cascade annulation of 2-ethynylaldehyde hydrazones with α-bromo-carbonyls for the synthesis of various cyclohexylidene-hydrazine-fused polycyclic compounds is described. This protocol is characterized by a broad substrate scope, mild conditions and amenability to gram-scale synthesis.

Metal-Free Radical Oxidative Cyclization of o-Azidoaryl Acetylenic Ketones with Sulfinic Acids To Access Sulfone-Containing 4-Quinolones.

A novel one-pot synthesis of sulfone-containing 4-quinolones with easily available sulfinic acids as sulfonylating precursors is described. This reaction is characterized by mild reaction conditions, high functional-group tolerance and amenability to gram-scale synthesis.

Oxidative C(sp(2))-H Phosphonation of Aldehyde Hydrazones.

A K2S2O8/Cu(OAc)2-mediated oxidative C-H/P-H cross-coupling of aldehyde hydrazones with diphenylphosphine oxide for the direct preparation of functionalized α-iminophosphine oxides is reported. The reaction shows good functional group tolerance and proceeds smoothly under mild conditions. This strategic protocol for C-P bond formation is facilitated by a net oxidative aminyl radical-polar crossover process.

Synthesis of isoxazoline-functionalized phenanthridines via iminoxyl radical-participated cascade sequence.

Readily accessible ß,γ-unsaturated ketoximes reacted with 2-arylphenylisonitriles under the conditions of t-BuOOH and n-Bu4NI to give isoxazoline functionalized phenanthridines via tandem intramolecular/intermolecular C-O/C-C/C-C bond formation. The reaction involves the initial generation of iminoxyl radicals from the oxidation of ß,γ-unsaturated ketoximes by t-BuOOH and n-Bu4NI followed a cascade radical cyclization/addition/cyclization sequence.

Transition from π radicals to σ radicals: substituent-tuned cyclization of hydrazonyl radicals.

Hydrazonyl radicals are known for their p-electronic structures; however, their s-electronic structures have not been reported as yet. Herein, we show that readily accessible b,g- and g,d-unsaturated N-trichloroacetyl and Ntrifluoroacetyl hydrazones can be conveniently converted into hydrazonyl s radicals, which subsequently undergo 5-exo-trig radical cyclization at the N1 or N2 atom to form pyrazolines and azomethine imines, respectively.