Photooxidative Reaction of ß-Oxoamides with Amines for the Synthesis of Pyrrolin-4-ones under External Photocatalyst-Free Conditions.

The incorporation of oxygen atoms from air under aerobic conditions plays an important role in organic synthesis. Herein, Brønsted acids are found to be a two-in-one strategic catalyst to transform enamines from ß-oxoamides and amines to pyrrolin-4-ones without an external photocatalyst under visible-light conditions. The Brønsted acid can inhibit the C-C bond fragmentation of the [2 + 2] adduct from enamine and 1O2, but most importantly, it can form photosensitizers with enamine and pyrrolin-4-one product by acidochromism to promote the 1O2 generation.

Discovery of the Quinoxalinone-B(C6F5)3·H2O Combo as a Photocatalyst by Acidochromism Strategy: Aerobic Oxidation of Alcohol, Alkene, and Thiols.

Modification of photocatalyst reactivity through intermolecular interactions represents a straightforward and convenient strategy for catalyst designation. Herein, we reported that upon the addition of B(C6F5)3·H2O, the oxidation potential of quinoxalinone increased remarkably, enabling the photoredox aerobic oxidation of alcohol, thiols, and alkenes toward carbonyl compounds and dithioethers under visible light conditions. Mechanistic studies, including X-ray structure analysis, cyclic voltammetry, electron paramagnetic resonance measurements, UV-vis absorption, and fluorescence spectra, revealed that the quinoxalinone-B(C6F5)3·H2O combo could serve as a versatile photocatalyst for both energy transfer and single electron transfer processes.

Synergistic effect of hydrogen bonds and π-π interactions of B(C6F5)3·H2O/amides complex: Application in photoredox catalysis.

B(C6F5)3·H2O has been long recognized as a common Brønsted acid. The lack of X-ray crystal structure of B(C6F5)3·H2O with other substrates has greatly limited the development of a new catalytic mode. In this work, a complex of B(C6F5)3·H2O and amide 2-phenyl-3,4-dihydroisoquinolin-1(2H)-one with hydrogen bonds and π-π interactions is characterized by X-ray diffraction. Such noncovalent interactions in solution also exist, as verified by NMR, UV-Vis absorption, and fluorescence emission measurements. Moreover, the mixture of amide 2-phenyl-3,4-dihydroisoquinolin-1(2H)-one and B(C6F5)3·H2O, instead of other tested Brønsted acids, shows a tailing absorption band in the visible light region (400-450 nm). Based on the photoactive properties of the complex, a photoredox catalysis is developed to construct α-aminoamides under mild conditions.

Oxidative cross-coupling of quinoxalinones with indoles enabled by acidochromism.

An oxidative cross-coupling of quinoxalinones with indole derivatives via B(C6F5)3·H2O induced acidochromism of quinoxalinone derivatives was developed under mild and external photocatalyst-free conditions. The reaction shows excellent substrate scope, accommodating a wide range of functional groups. The usefulness of this strategy was demonstrated by the synthesis of the natural products Azacephalandole A and Cephalandole A in high yields. Moreover, the products are fluorophores showing prevalent fluorescence properties with a wide emission range and good relative quantum yields.

Highly E-Selective Olefin Synthesis Catalysed by Novel Quinoxalinone Photocatalyst under Visible Light Conditions.

In photo-induced olefin synthesis, the photocatalysts with high triplet energy could cause the isomerization of olefins. This study demonstrates a new quinoxalinone photocatalytic system for highly stereoselective alkenes preparation from alkenyl sulfones and alkyl boronic acids. Our photocatalyst could not convert the thermodynamically favored E-olefin to Z-olefin, guaranteeing the high E-configuration selectivity of the reaction. There is weak interaction between boronic acids and quinoxalinone according to NMR experiments, probably decreasing the oxidation potential of boronic acids. This system can be further extended to the allyl and alkynyl sulfones to give corresponding alkenes and alkynes.

The B(C6F5)3·H2O promoted synthesis of fluoroalkylated 3,3',3''-trisindolylmethanes from fluorocarboxylic acids and indoles.

Trisindolylmethanes (TIMs) exist in many bioactive natural products and are frequently applied in medicinal chemistry and materials science. Herein, a simple and efficient protocol promoted by B(C6F5)3·H2O for the synthesis of their fluoroalkylated analogues, fluoroalkylated 3,3',3''-TIMs, is reported for the first time. Easily accessible fluorocarboxylic acids are utilized as the fluoroalkyl sources, exhibiting an obvious fluorine effect. This convenient and green process features mild and metal-free conditions, easy scale-up, and an environmentally friendly byproduct.

Divergent Synthesis of 2-Cyanoaryl Carbamate and 2-Cyanoaryl Urea Derivatives via Hypervalent Iodine-Induced C-C Bond Cleavage.

Divergent synthetic methods for transforming isatins to 2-cyanoaryl carbamate and 2-cyanoaryl urea derivatives were developed using ammonium carbamate as the nitrogen source and iodobenzene diacetate as the oxidant. This reaction features mild conditions, broad substrate scope, and moreover, the use of toxic cyano-containing compounds is avoided.

Synthesis of (2-(Quinolin-2-yl)phenyl)carbamates by a One-Pot Friedel-Crafts Reaction/Oxidative Umpolung Aza-Grob Fragmentation Sequence.

Utilizing the easily available isatin-based propargyl amines prepared from isatins, terminal alkynes, and anilines, (2-(quinolin-2-yl)phenyl)carbamates were prepared by a one-pot reaction in sequence, combining the gold-catalyzed Friedel-Crafts cyclization, oxidative umpolung aza-Grob fragmentation, and nucleophilic addition. In this process, gold-catalyzed cyclization of isatin-based propargyl amines gave 1'H-spiro[indoline-3,2'-quinolin]-2-ones, which were oxidized in situ by hypervalent iodine via the aza-Grob fragmentation to afford isocyano intermediates 2-(2-isocyanatophenyl)quinolines. Followed by the nucleophilic addition with alcohol solvents, (2-(quinolin-2-yl)phenyl)carbamates were synthesized. This procedure features easy operation, a wide substrate scope, and mild conditions.

B(C6F5)3-Catalyzed Electron Donor-Acceptor Complex-Mediated Aerobic Sulfenylation of Indoles under Visible-Light Conditions.

An efficient B(C6F5)3-catalyzed aerobic oxidative C-S cross-coupling reaction of thiophenol with indoles was developed, affording a wide range of diaryl sulfides in good yields. An electron donor-acceptor complex between B(C6F5)3 and indoles was formed, facilitating the photoinduced single-electron transfer (SET) from indole substrates to the B(C6F5)3 catalyst. This protocol demonstrates a new reaction model using B(C6F5)3 as a single-electron oxidant.

Lewis Acid Catalyzed [4 + 2] Cycloaddition of N-Tosylhydrazones with ortho-Quinone Methides.

A formal [4 + 2] cycloaddition of N-tosylhydrazones with ortho-quinone methides was developed, affording the facile synthesis of diverse 1,3-oxazine derivatives under mild conditions. In this transformation, N-tosylhydrazones are used as a 1,2-dipole synthon under base-free conditions. Moreover, the substrate scope is broad, and the products are formed with high diastereoselectivities in most of the cases.

Boron-Catalyzed Azide Insertion of α-Aryl α-Diazoesters.

A challenging metal-free azide insertion of α-aryl α-diazoesters in the presence of B(C6F5)3 (5 mol %) was developed for the first time. The reaction features an easy operation, wide substrate scope, and mild conditions and affords the corresponding products in moderate to high yields. More importantly, alkene and alkyne functional groups were well tolerated because no cyclopropanation or cyclopropenation was observed. Furthermore, the corresponding azide products could be converted to primary amines or 1,2,3-triazole derivatives after simple transformations.

Site-Selective α-Alkoxyl Alkynation of Alkyl Esters Mediated by Boryl Radicals.

A novel method for site-selective C-H functionalization of ethyl acetate mediated by pyridine-boryl radicals is presented, delivering a variety of 4-phenylbut-3-yn-2-yl acetate derivatives under mild conditions. A distinguishing feature of this reaction is that the pyridine-ligated boryl radicals can abstract the inactive α-hydrogen of the alkoxyl group instead of the α-hydrogen of carbonyl groups described in a previous report using amine-ligated boryl radicals. Significantly, substrates with halogen atoms are compatible under the reaction conditions.

Alkylation of Allyl/Alkenyl Sulfones by Deoxygenation of Alkoxyl Radicals.

A challenging deoxygenation of alkoxyl radicals from readily accessible alcohol derivatives was developed, affording facile synthesis of functionalized alkenes with good functional group tolerance under mild reaction conditions. Because alkoxyl radicals can easily undergo ß-fragmentations or hydrogen abstractions, this new strategy for deoxygenation of alkoxyl radicals is highly valuable. Moreover, mechanistic studies revealed that the electron-neutral phosphine acts as the deoxygenation reagent.

Boron-Catalyzed O-H Bond Insertion of α-Aryl α-Diazoesters in Water.

A catalytic, metal-free O-H bond insertion of α-diazoesters in water in the presence of B(C6F5)3· nH2O (2 mol %) was developed, affording a series of α-hydroxyesters in good to excellent yields. The reaction features easy operation and wide substrate scope, and importantly, no metal is needed as compared with the conventional methods. Significantly, this approach further expands the applications of B(C6F5)3 under water-tolerant conditions.

Boryl Radicals-Triggered Selective C-H Functionalization for the Synthesis of Diverse Phenanthridine Derivatives.

A boryl radical-triggered C-H functionalization of aliphatic ethers/amines or DMF with isocyanides is developed to deliver diverse phenanthridine derivatives in good to excellent yields. The substrate scope is broad, and a wide range of functional groups are tolerated under the standard conditions. The rapid removal of HBPin species by 4-cyanopyridine 1-oxide provides the driving force for this reaction. This new method should make boryl radicals widely applicable in organic synthesis.

Dual-role of PtCl2 catalysis in the intramolecular cyclization of (hetero)aryl-allenes for the facile construction of substituted 2,3-dihydropyrroles and polyheterocyclic skeletons.

A Pt(ii)-catalyzed cyclization of (hetero)aryl-allenes has been developed, providing controllable synthesis of substituted 2,3-dihydropyrroles and polyheterocyclic skeletons. Another notable feature of this method is the dual-role of the Pt(ii) catalyst: initiation of the migration of the (hetero)arylmethylene group and the subsequent Friedel-Crafts type annulation.

Gold(I)-Catalyzed Cycloisomerization of ortho-(Propargyloxy)arenemethylenecyclopropanes Controlled by Adjacent Substituents at Aromatic Rings.

Gold(I)-catalyzed cycloisomerization of ortho-(propargyloxy)arenemethylenecyclopropanes afforded two different types of products, that is, products of methylenecyclopropane migration and cycloisomerization products of the methylenecyclopropane moiety, controlled jointly by electronic and steric effects of the adjacent substituents. Furthermore, the corresponding cycloisomerization products could be also produced in an enantiomerically enriched manner.

Rhodium/Silver Synergistic Catalysis in Highly Enantioselective Cycloisomerization/Cross Coupling of Keto-Vinylidenecyclopropanes with Terminal Alkynes.

A rhodium/silver synergistic catalysis has been established, enabling cycloisomerization/cross coupling of keto-vinylidenecyclopropanes (VDCPs) with terminal alkynes toward the regio- and enantioselective formation of diversified tetrahydropyridin-3-ol tethered 1,4-enynes in good yields and high ee values. In this synergistic catalysis, Rh(I) and Ag(I) catalysts selectively activate keto-VDCP substrates and terminal alkynes to generate the π-allyl Rh(III) complex of oxa-rhodacyclic intermediate and Ag alkynyl intermediate, respectively. The rapid transmetalation of alkynyl groups from Ag to Rh is proposed to play a key role in realizing the regioselective cleavage of the distal bond of the three-membered ring in this transformation.

Gold-Catalyzed Fluorination-Hydration: Synthesis of α-Fluorobenzofuranones from 2-Alkynylphenol Derivatives.

The Au(I) -catalyzed fluorination-hydration of 2-alkynylphenol derivatives in the presence of Selectfluor [1-chloromethyl-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octane bis(tetrafluoroborate)] has been developed. This method provides straightforward access to α-fluorobenzofuranones with the construction of C-O, C=O, and C-F bonds in a single step on the basis of an Au(I) /Au(III) redox catalytic cycle. Several control experiments, including the asymmetric variant of this reaction, were also conducted to gain insight into the reaction mechanism.

Gold(i)-catalyzed dehydrogenative cycloisomerization of 1,5-enynes.

The gold(i)-catalyzed dehydrogenative cycloisomerization of cyclopropane-tethered 1,5-enynes proceeded smoothly to give multisubstituted benzene derivatives in good to excellent yields. Synthetically important benzocyclobutenes can be produced in high yields in the presence of a gold(i) catalyst and DDQ. Furthermore, this reaction also works very well for non-cyclopropane tethered 1,5-enynes.