Photoinduced Pd-Catalyzed Dearomative 2,5-Difunctionalizition of Furans via Cascade C-C/C-O Bond Formation.

We report an efficient and mild approach for radical dearomatization via photoinduced palladium-catalyzed reaction of three components (i.e., furans, alcohols, and bromoalkanes). In this strategy, various functionalized spiro-heterocycles were prepared from furans in one step via cascade C-C/C-O bond formation under redox neutral conditions.

Radical-Dearomative Generation of Cyclohexadienyl Pd(II) toward the 3D Transformation of Nonactivated Phenyl Rings.

Traditional palladium-catalyzed dearomatization of (hetero)arenes takes place via an ionic pathway and usually requires elevated temperatures to overcome the energy barrier of the dearomative insertion step. Herein, a combination of the radical and two-electron pathways is disclosed, which enables room temperature dearomative 3D transformations of nonactivated phenyl rings with Pd(0) as the catalyst. Experimental results together with density functional theory (DFT) calculations indicate a versatile π-allyl Pd(II) species, cyclohexadienyl Pd(II), possibly is involved in the dearomatization. This species is generated by combining the cyclohexadienyl radical and Pd(I). The cyclohexadienyl Pd(II) provides chemoselective (carboamination and trieneylation), regioselective (1,2-carboamination), and diastereoselective (carbonyl-group directed face selectivity) conversions.

Intramolecular Cobalt/Visible Light Cocatalyzed Reductive Coupling of Unactivated Arenes with Unactivated Alkenes.

A protocol for the intramolecular reductive coupling of unactivated arenes with unactivated alkenes has been developed with the aid of a cooperative visible light/cobalt catalytic system. This coupling is achieved via radical cascade cyclization using amines as terminal reducing reagents and water as the main hydrogen source. In their form, readily available N-allyl benzamides are converted to the corresponding spiro cyclohexadiene-lactam or ß-phenethylamine analogues in moderate to excellent yields.

Template-Oriented Polyaniline-Supported Palladium Nanoclusters for Reductive Homocoupling of Furfural Derivatives.

Developing well-defined structures and desired properties for porous organic polymer (POP) supported catalysts by controlling their composition, size, and morphology is of great significance. Herein, we report a preparation of polyaniline (PANI) supported Pd nanoparticles (NPs) with controllable structure and morphology. The protocol involves the introduction of MnO2 with different crystal structures (α, ß, γ, δ, ϵ) serving as both the reaction template and the oxidant. The different forms of MnO2 each convert aniline to a PANI that contains a unique regular distribution of benzene and quinone. This leads to the Pd/PANI catalysts with different charge transfer properties between Pd and PANI, as well as different dispersions of the metal NPs. In this case, the Pd/ϵ-PANI catalyst greatly improves the turnover frequency (TOF; to 88.3 h-1 ), in the reductive coupling of furfural derivatives to potential bio-based plasticizers. Systematic characterizations reveal the unique oxidation state of the support in the Pd/ϵ-PANI catalyst and coordination mode of Pd that drives the formation of highly dispersed Pd nanoclusters. Density functional theory (DFT) calculations show the more electron rich Pd/PANI catalyst has the lower energy barrier in the oxidative addition step, which favors the C-C coupling reaction.

Visible-Light-Induced Diradical-Mediated ipso-Cyclization towards Double Dearomative [2+2]-Cycloaddition or Smiles-Type Rearrangement.

When mono-radical ipso-cyclization of aryl sulfonamides tend to undergo Smiles-type rearrangement through aromatization-driven C-S bond cleavage, diradical-mediated cyclization must perform in a distinct reaction pathway. It is interesting meanwhile challenging to tune the rate of C-S bond cleavage to achieve a chemically divergent reaction of (hetero) aryl sulfonamides in a visible-light induced energy transfer (EnT) reaction pathway involving diradical species. Herein a chemically divergent reaction based on the designed indole-tethered (hetero)arylsulfonamides is reported which involves a diradical-mediated ipso-cyclization and a controllable cleavage of an inherent C-S bond. The combined experimental and computational results have revealed that the cleavage of the C-S bond in these substrates can be controlled by tuning the heteroaryl moieties: a) If the (hetero)aryl is thienyl, furyl, phenanthryl, etc., the radical coupling of double dearomative diradicals (DDDR) precedes over C-S bond cleavage to afford cyclobutene fused indolines by double dearomative [2+2]-cycloaddition; b) if the (hetero)aryl is phenyl, naphthyl, pyridyl, indolyl etc., the cleavage of C-S bond in DDDR is favored over radical coupling to afford biaryl products.

Photoinduced Pd-Catalyzed Csp2-H/Csp3-H Dehydrocoupling Reaction Employing Polyhaloaromatics as the Dehydrogenating Agent.

A mild strategy for intermolecular cross-dehydrocoupling of Csp2-H bonds and Csp3-H bonds has been developed with the aid of photoinduced Pd catalysis. Polyhalogenated arenes can be used as the efficient dehydrogenating agent, which enables multifold transfer of carbon radical to avoid the production of stoichiometric or excess wasted arenes. In this strategy, substituted styrenes and N-arylacrylamides with simple ethers or amides as the coupling partners gives the corresponding internal alkenes and benzolactams with moderate to good yield.

LiCl-Mediated and Palladium-Catalyzed Oxidative Cyclization of Furan-Ynes via Dearomatizing Alkoxyalkenylation of Furan.

A LiCl-mediated and palladium(II)-catalyzed oxidative cyclization of furan-ynes via dearomatizing alkoxyalkenylation of furan is reported to afford polyfunctionalized spiro-dihydrofurans with diastereospecification and high Z/E selectivity. This protocol is likely to involve chloropalladation of alkynes, subsequent intramolecular dearomatizing alkenylation of furan, and final O-allylation. The density functional theory (DFT) calculations demonstrated that the coordination of furan with dissolved Li+ weakens its nucleophilicity and promoted the Heck insertion, and dissolved Cl- promoted chloropalladation of alkynes.

Access to Polycyclic Thienoindolines via Formal [2+2+1] Cyclization of Alkynyl Indoles with S8 and K2S.

The syntheses of polycyclic thienoindolines bearing a dihydrothiophene or tetrahydrothiophene subunit have not been reported, despite the fact that such compounds may have interesting medicinal properties. Herein, we report a protocol for accessing polycyclic dihydrothiophenes by means of formal [2+2+1] intramolecular dearomatizing cyclization of alkynyl indoles with K2S and S8 as the sources of sulfide. In addition, tetrahydrothienoindolines were stereoselectively synthesized via a one-pot, two-step protocol involving AgNO3-catalyzed alkenyl dearomatization followed by two nucleophilic addition reactions involving K2S.

Synthesis of Highly Conjugated Functionalized 2-Pyridones by Palladium-Catalyzed Aerobic Oxidative Dicarbonation Reactions of N-(Furan-2-ylmethyl) Alkyne Amides and Alkenes as Coupling Partners.

A mild, step-economical method for the synthesis of highly conjugated functionalized 2-pyridones from N-(furan-2-ylmethyl) alkyne amides is reported. This method involves Pd-catalyzed aerobic oxidative dicarbonation reactions of alkynes with carbon nucleophiles of a furan ring and an acrylate or styrene as coupling partners. The UV-vis absorption spectra of some of the 2-pyridones indicated that they absorbed shortwave radiation, suggesting their potential utility for filtration of such radiation.

CuCl2-catalyzed highly stereoselective and chemoselective reduction of alkynyl amides into α,ß-unsaturated amides using silanes as hydrogen donors.

A CuH-catalyzed Z-selective partial reduction of alkynyl amides to afford α,ß-unsaturated amides using silane as the hydrogen donor is developed. This reaction is carried out under mild conditions and able to accommodate a broad scope of alkynyl amides including those bearing a terminal carbon-carbon double bond or triple bond, affording alkenyl amides with high stereoselectivity and excellent yields.

Iron-Catalyzed Oxidative Decarbonylative α-Alkylation of Acyl-Substituted Furans with Aliphatic Aldehydes as the Alkylating Agents.

A protocol for FeCl2-catalyzed oxidative decarbonylative α-alkylation of acyl furans using alkyl aldehydes as the alkylating agents has been developed. This protocol affords α-alkyl-α-acylfurans in moderate to good yields in a practical and sustainable fashion. Mechanistic studies suggest that the reaction proceeds via generation of an alkyl radical from the alkyl aldehyde, addition of the radical to the furan ring, and subsequent rearomatization.

Direct Alkoxycarbonylation of Heteroarenes via Cu-Mediated Trichloromethylation and In Situ Alcoholysis.

We report an efficient approach for direct alkoxycarbonylation of furans as well as other heteroarenes via a one-step copper-mediated reaction of three components (i.e., heteroarene, alcohol, and CHCl3). The copper additive was confirmed to simultaneously promote the reaction in three pathways: oxidant cracking, single electron transfer, and alcoholysis. By means of this protocol, various functionalized furancarboxylates and other heteroarenecarboxylates were facilely obtained in moderate to good yields.

Access to N-unprotected 2-amide-substituted indoles from Ugi adducts via palladium-catalyzed intramolecular cyclization of o-iodoanilines bearing furan rings.

A variety of N-unprotected 2-amide-substituted indoles were synthesized from readily available furfural-based Ugi adducts in moderate to good yields via palladium-catalyzed intramolecular cyclization of o-iodoanilines bearing furan rings. These reactions involved a cascade sequence consisting of dearomatizing arylation, opening of the furan ring, and deprotection of the N atom.

CuH-Catalyzed Synthesis of 3-Hydroxyindolines and 2-Aryl-3H-indol-3-ones from o-Alkynylnitroarenes, Using Nitro as Both the Nitrogen and Oxygen Source.

CuH-catalyzed diasterospecific synthesis of 3-hydroxyindolines and 2-aryl-3H-indol-3-ones have been developed from o-alkynylnitroarenes in the presence of hydrosilane as the reductant. The protocol employs nitro as both nitrogen and oxygen sources for the intramolecular simultaneous construction of C-N and C-O bonds.

Access to Polycyclic Sulfonyl Indolines via Fe(II)-Catalyzed or UV-Driven Formal [2 + 2 + 1] Cyclization Reactions of N-((1H-indol-3-yl)methyl)propiolamides with NaHSO3.

A variety of structurally novel polycyclic sulfonyl indolines have been synthesized via FeCl2-catalyzed or UV-driven intramolecular formal [2 + 2 + 1] dearomatizing cyclization reactions of N-(1 H-indol-3-yl)methyl)propiolamides with NaHSO3 in an aqueous medium. The reactions involve the formation of one C-C bond and two C-S bonds in a single step.

Three-Component Ring-Opening Reactions of Cyclic Ethers, α-Diazo Esters, and Weak Nucleophiles under Metal-Free Conditions.

A protocol for three-component reactions of cyclic ethers, α-diazo esters, and weak nitrogen, oxygen, carbon, and sulfur nucleophiles (p Ka = 2.2-14.8) to afford a variety of structurally complex α-oxyalkylated esters is reported. These reactions involve intermolecular activation of the cyclic ether (present in excess) by the α-diazo ester to form an oxonium ylide under metal-free conditions, followed by ring opening by the nucleophile.

Tandem Achmatowicz Rearrangement and Acetalization of 1-[5-(Hydroxyalkyl)-furan-2-yl]-cyclobutanols Leading to Dispiroacetals and Subsequent Ring-Expansion to Form 6,7-Dihydrobenzofuran-4(5 H)-ones.

Herein, we report a one-pot protocol for the synthesis of dispiroacetals 4 bearing a cyclobutane motif via tandem Achmatowicz rearrangement and acetalization of 1-[5-(hydroxyalkyl)-furan-2-yl]-cyclobutanols 3 with m-CPBA as the oxidant and AgSbF6 as an additive to promote the cyclization step in an aqueous medium. Dispiroacetals 4 could subsequently undergo Lewis acid-catalyzed ring expansion and skeletal rearrangement to afford 6,7-dihydro-5 H-benzofuran-4-ones 5.

Synthesis of N, O-Spiroacetals and α-Arylfurans via Pd-Catalyzed Aerobic Oxidative 2,5-Aminoarylation and α-Arylation of N-[3-(2-Furanyl)propyl]- p-toluenesulfonamides with Boronic Acids.

Unsaturated N, O-spiroacetals and α-arylfurans were synthesized via palladium-catalyzed aerobic oxidative coupling reactions between N-[3-(2-furanyl)propyl]- p-toluenesulfonamides and boronic acids, with KF and KOAc as the respective additives. These reactions involve an unprecedented dearomatizing 2,5-aminoarylation and a direct α-arylation of furan rings, respectively, with O2 as the terminal oxidant.

Access to Densely Functionalized Chalcone Derivatives with a 2-Pyridone Subunit via Pd/Cu-Catalyzed Oxidative Furan-Yne Cyclization of N-(2-Furanylmethyl) Alkynamides under Air.

A protocol for synthesis of chalcone derivatives with a 2-pyridone subunit from N-(2-furanylmethyl) alkynamides is reported. This synthesis involves Pd/Cu-catalyzed oxidative furan-yne cyclization at room temperature in air and may proceed via nucleopalladation of the alkyne to form a vinylpalladium intermediate, with a furan ring acting as the nucleophile.

Aerobic oxidative α-arylation of furans with boronic acids via Pd(ii)-catalyzed C-C bond cleavage of primary furfuryl alcohols: sustainable access to arylfurans.

Aerobic oxidative α-arylation of furans with boronic acids via Pd(ii)-catalyzed C-C bond cleavage of primary furfuryl alcohols provides sustainable access to arylfurans. This protocol opens a new avenue for the transformation of readily available furans into other useful compounds.