Herein we reported a direct synthesis series of indolines through cyclization of tertiary aryl amines with iodonium ylides. This cyclization reaction occurred under sole visible-light irradiation at room temperature without the addition of any photocatalysts and additives. Preliminary mechanism studies revealed that an electron donor-acceptor (EDA) complex between iodonium ylides and tertiary aryl

A silver-catalyzed protocol for the synthesis of 3-(1H-isochromen)-chromones is described. The method involves an initial 6-endo-dig cyclization of o-alkynylbenzaldehydes and domino C−H alkylation and chromone annulation of the o-hydroxyarylenaminones, which enables the installation of 1H-isochromen and chromone in a single structure. This synthetic strategy is advantageous for the excellent regioselectivity

Various widely applied compounds contain cyano-groups, and this functional group serves as a chemical handle for a whole range of different reactions. We report a cyanide free chemoenzymatic cascade for nitrile synthesis. The reaction pathway starts with a reduction of carboxylic acid to aldehyde by carboxylate reductase enzymes (CARs) applied as living cell biocatalysts. The second – chemical – step

Carboranes, a three-dimensional class of carbon-boron molecular clusters with remarkable electronic, physical, chemical characteristics, have proved as useful building blocks in boron neutron capture therapy agents, supramolecular design, optoelectronics, nanomaterials and organometallic/coordination chemistry. Thus, various organic modifications of the B-H and C-H functionalities in carboranes have

Herein, we report the synthesis of functionalized dihydro-benzo[b]fluorenones through a manganese-mediated cascade radical cyclization of β-alkynyl propenones [1,6-enynes] with arylboronic acids. In the present strategy, the in-situ generated aryl radical undergoes chemo-selective addition followed by 5-exo-trig cyclization. The reaction is emphasized by high atom- and step-economy with the construction

A approach for the construction of furanochromanone skeletons has been developed through a DABCO-catalyzed cascade reaction with good yields (up to 83%) and high diastereoselectivity (>20:1 dr). Notably, the asymmetric catalytic version of this reaction was further studied, obtaining furanochromanones bearing four contiguous stereogenic centers with excellent enantio- and diastereoselectivity (up to

1,3-Dienes are prevalent substructures in biologically active molecules and versatile building blocks in synthetic chemistry. Herein, using Lewis acids promoted dual 1,3-sulfur rearrangements, we developed an approach for the direct synthesis of 1,3-dithianyl substituted dienes. This method enabled the synthesis of tri- and tetra-substituted 1,3-dienes with high stereoselectivity and good yield under

Three-dimensional aliphatic fused and bridged rings are key pharmacophores in drugs and bioactive natural products. Here, we reported an organocatalytic visible-light induced dearomative cycloaddition of (hetero)arenes, with organic light-emitting diode material 4CzIPN or readily accessible thioxanthone as photocatalyst. A series of cyclobutane-fused polycyclic structures and bridged bicyclo scaffolds

This study reports the synthesis of diverse β-functionalized ketones from readily available 1-arylallylic alcohols in the presence of (trimethylsilyl)methylpotassium (TMSCH2K). The reaction proceeded via the formation of the highly nucleophilic dipotassio α,β-dianion as the key intermediate, which served as a metal homoenolate equivalent. This protocol also allowed the one-pot synthesis of α,β-difunctionalized

The catalytic enantioselective allenylation of ketimines derived from isatins is described. Products with high regio- and enantioselectivities were obtained in the presence of a bis(imidazoline)-palladium catalyst. The obtained products were then converted to various chiral amines. The stereoselectivity origin was revealed by DFT calculations of the transition state.

Herein we report the synthesis of 3-aryl oxindoles having trifluoromethylated quaternary stereocenters through the catalyst free arylation of 3-trifluoromethyl,3-tosyloxy oxindoles with anisoles. The transformation proceeds via electrophilic 3-(trifluoromethyl)-2H-indolium intermediate (Michael acceptor), which is generated by the heterolytic cleavage of C-OTs bond under metal-free conditions in PEG-400

A rhodium-catalyzed cascade cross-coupling/spirocyclization/formal [4+2] cycloaddition reaction of 3-(2-isocyanoethyl)indoles with aromatic azides is developed, providing a general synthetic protocol to polycyclic spiroindolines bearing a pentasubstituted guanidine moiety with moderate to excellent yields. This transformation is highly efficient since one C-C, one C=N, three C-N bonds as well as two

The visible-light-induced synthesis of 5-phosphoryl-functionalized pyrroles has been established by eosin Y catalysis, and different electron-donating or electron-withdrawing group substituted secondary H-phosphine oxides and phenacylmalononitriles showed reactivity toward the reaction, affording the cascade phosphinoylation/cyclization products in 82-98% yields via P-C/C-N annulation. Step-by-step

Metallaphotoredox processes have emerged as powerful methods for C-C bond formations. The Ni-photoredox catalyzed desulfurative cross-coupling of thiol derivatives with aryl bromides has now been established. This procedure provides access to simple and complex unsymmetrical diarylmethane molecules under mild reaction conditions with a broad functional group tolerance. The key steps of the reaction

In this manuscript, we report a radical type ring-opening of sulfonium salts with heteroarenes under visible light conditions. This developed method does not require noble metal photocatalysts, or stoichiometric amount of external oxidants, and has a application prospect in the synthesis of organosulfur compounds and bioactive molecules. This radical type ring-opening photocatalytic system could inspire

We describe a silver catalyzed [3+2] diastereoselective annulation of p-quinamines and ketenimine zwitterionic salts, leading to anti-3-substituted hydroindolin-2-imines under mild conditions. Ketenimine zwitterionic salts participate in the [3+2] cycloadditions as a monoolefin (2π-system). The relative stereoselectivity of the reaction was regulated by the tert-butyl ester. This protocol is complementary

L-threonine aldolase (LTA) is a vital tool for the production of β-hydroxy-α-amino acids, important pharmaceutical intermediates with two chiral centres. However, the trade-off between activity and diastereoselectivity seriously hinders the application of LTA. Here, microenvironment of the proton transfer was regulated to improve the enzyme activity while avoiding the loss of diastereoselectivity.

Chiral bis-oxalamide (CBOA)/rare-earth metal complexes-catalyzed asymmetric inverse-electron-demand oxa-hetero-Diels–Alder (HDA) reactions were investigated under mild reaction conditions, which was performed between β,γ-unsaturated α-ketoesters and various electron-riched dienophiles, such as cyclopentadiene, 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, tetrahydropyridine as well as phenyl(vinyl)sulfane

Abstract. An acceptorless dehydrogenative methodology for the synthesis of amides and carbonyls from hemiaminal and alcohols in the presence of manganese(I) based photocatalyst is developed. Several aromatic, aliphatic, heterocyclic aldehydes and primary aryl amines as well as secondary alkyl amines were coupled, providing the corresponding amides. The methodology was also extended for dehydrogenation

We herein describe the direct Suzuki–Miyaura coupling of dan-substituted, saturated organoboron compounds. Despite its Lewis acidity-diminished character of the boron center, cyclopropyl–B(dan) can be activated by t-BuOK to undergo transmetalation with a palladium complex. The increased s-character of the C–B(dan) bond as compared with other alkyl–B(dan) should be the key to the reaction.

Optically pure lactams have a wide diversity of applications, one of which is serving as important intermediates in the synthesis of agricultural bioactive compounds or pharmaceuticals. Efficient stereoselective synthesis of chiral lactams with low-cost amine donors under mild conditions is desired for manufacturing of these important chemicals. Herein, a two-step chemo-enzymatic strategy has been

A direct (organo)catalytic method for the synthesis of chiral selenylated δ-lactones via [4+2] annulation of selenyl vinyl ketones with enals has been achieved. The C5-selenylated dihydropyranones were obtained in 54–88% yield with 90–99% enantioselectivity.

A copper-catalyzed multicomponent oxysulfonylation of alkenes with cyclobutanone oxime esters and hydroxamic acids via the insertion of sulfur dioxide has been developed. This reaction uses K2S2O5 as the sulfur dioxide surrogate and the in situ generated amidoxyl radical as radical interceptor, thus providing a direct approach to β-amidoxy sulfones in 35–90% yields. Mechanistic studies revealed that