An efficient protocol for the generation of amines by palladium-catalyzed nucleophilic benzylic addition 2-methyl-substituted azaarenes to N-sulfonyl aldimines under neutral conditions via C−H bond activation has been developed. This reaction represents a very methodology synthesis heterocycle-containing and thus opens new way access through activation.

A novel and efficient Rh/O2 catalytic system has been developed shown to catalyze highly oxidative C-H activation/annulation reactions, producing a broad range of isoquinolinium salts with high turnover numbers (up 740). Mechanistic studies provided strong evidence facile oxidation Rh(I) Rh(III) by molecular oxygen facilitated acid.

A novel PPh(3)-catalyzed (4 + n) annulation of 2-(acetoxymethyl)buta-2,3-dienoates 1c-e with 1,n-bisnucleophiles (n = 1, 2) has been developed to provide a facile synthetic method for cyclopentene and 1,2,3,6-tetrahydropyridazine derivatives. The acetate group 2-(acetoxymethyl)buta-2,3-dienoate is crucial the formation 1,4-biselectrophilic intermediate C, which recognized be 1,4-biselectrophile that can react 1,n-bisnucleophiles. Deuterium studies also suggest reaction pathway involves...

Adverse side effects of drug–drug interactions induced by human cytochrome P450 (CYP) inhibition is an important consideration, especially, during the research phase drug discovery. It highly desirable to develop computational models that can predict inhibitive effect a compound against specific CYP isoform. In this study, inhibitor predicting were developed for five major isoforms, namely 1A2, 2C9, 2C19, 2D6, and 3A4, using combined classifier algorithm on large data set containing more...

Asymmetric catalytic C–C coupling reactions via C–H bond activation are currently among the most attractive and powerful tools in synthetic organic chemistry. In past few decades, a variety of asymmetric have been reported. Compared with traditional formation reactions, activation/C–C strategies more advantages terms power cost-effectiveness. this review, after short introduction recent studies on reviewed, an emphasis enantioselective cross-dehydrogenative-coupling, activation/olefin...

Nitrogen revives: Cyclic N-acyliminium ions were generated from α,β-unsaturated γ-lactams (1) and underwent intermolecular addition by indole nucleophiles (2) under the catalysis of a chiral Brønsted acid (3). A variety N-functionalized derivatives containing pyrrolidinone moiety (4) assembled with high enantioselectivity. Bn=benzyl.

High enantioselectivities can be achieved using an appropriate chiral base/achiral ligand combination in Pd⁰-catalyzed C(sp³)–H activation.

The first organocatalyzed asymmetric dearomative cycloaddition between 2-nitrobenzofurans and isatin-derived Morita-Baylis-Hillman carbonates has been developed. Using a modified cinchona alkaloid as the catalyst, series of structurally diverse cyclopenta[ b]benzofuran derivatives with three contiguous stereocenters, including spiro-quaternary chiral center, could be smoothly obtained in excellent results (all cases >20:1 dr, up to 99% yield 98% ee). utility this method was showcased by...

A copper-catalyzed umpolung of N-2,2,2-trifluoroethylisatin ketimines for the enantioselective 1,3-dipolar cycloaddition with benzo[b]thiophene sulfones was developed. Using a catalyst system consisting an (S,Sp)-tBu-Phosferrox ligand, Cu(OTf)2, and Cs2CO3, range pentacyclic spirooxindoles containing pyrrolidine benzo[b]sulfolane subunits were obtained in high efficiency excellent regio-, diastereo-, enantioselectivites under mild conditions. The practicality versatility reaction also demonstrated.

Acid test: With a Brønsted acid as the solvent, rhodium-catalyzed direct addition of aryl CH bonds to α,β-unsaturated ketones was realized under mild reaction conditions (see scheme). The may assist by interceding in conflict two proton-transfer events and averting substrate inhibition involved this type reaction. Detailed facts importance specialist readers are published "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted...

Abstract A rhodium(III)‐catalyzed direct selective C‐2 alkenylation reaction of indoles with alkenes has been developed molecular oxygen as the sole oxidant. The rhodium/oxygen catalytic system is applicable to a broad range and alkenes, which provides novel access various alkenylated pyrroles. magnified image

A novel copper(II)-catalyzed, regioselective C–H benzylation of enones with toluenes via radical triggered oxidative coupling has been developed. series and different substituents were successfully incorporated, providing a wide range α-benzylated TBP as oxidant by cleavage C(sp3)–H bond C(sp2)–H bond. Preliminary mechanistic study reveals benzylic carbon is generated, regioselectively reacts to deliver the corresponding products.

Previous enantioselective Pd0 -catalyzed C-H activation reactions proceeding via the concerted metalation-deprotonation mechanism employed either a chiral ancillary ligand, base, or bimolecular mixture thereof. This study describes development of new bifunctional ligands based on binaphthyl scaffold which incorporates both phosphine and carboxylic acid moiety. The optimal ligand provided high yields enantioselectivities for desymmetrizing C(sp2 )-H arylation leading to...

An enantioselective dearomative 1,3-dipolar cycloaddition of 2-nitrobenzothiophenes and isatin-derived azomethine ylides with a bifunctional hydrogen-bonding thiourea catalyst was established, giving polyheterocyclic compounds in excellent results (up to 99% yield, >20:1 dr for all cases up ee). The enantioselectivity could be reversed by the squaramide containing same chiral source as catalyst. DFT calculations revealed origin observed stereochemistry reversal enantioselectivity.

A nickel-catalyzed reductive cross coupling between organic iodides and thiosulfonates a selenosulfonate under mild conditions is disclosed.

An unprecedented visible-light-driven regioselective carbocarboxylation of 1,3-dienes with CO 2 using aryl and alkyl halides under mild conditions is reported herein.

A catalyst system consisting of a chiral phosphoramidite ligand and Pd2(dba)3·CHCl3 causes the decarboxylation 5-vinyloxazolidine-2,4-diones to generate amide-containing aza-π-allylpalladium 1,3-dipole intermediates, which are capable triggering dearomatization 3-nitroindoles for diastereo- enantioselective [3+2] cycloaddition, leading formation series highly functionalized pyrroloindolines containing three contiguous stereogenic centers with excellent results (up 99% yield, 88:12 dr, 96% ee).

A cooperative catalytic system established by the combination of an iron salt and a chiral Brønsted acid has proven to be effective in asymmetric Friedel-Crafts alkylation indoles with beta-aryl alpha'-hydroxy enones. Good excellent yields enatioselectivities were observed for variety enones indoles, particularly bearing electron-withdrawing group at para position phenyl ring (up 90 % yield 91 ee). The proton acid, Lewis activation site, as well inherent basic site hydrogen-bonding...

Abstract Biodegradable polyesters with various tacticities have been synthesized by means of stereoselective ring-opening polymerization racemic lactide and β-lactones but limited side-chain groups. However, synthesis functional remains challenging from O -carboxyanhydrides that abundant pendant Herein we report a powerful strategy to synthesize stereoblock the use photoredox Ni/Ir catalysts selected Zn complex an achiral ligand. The obtained copolymers are highly isotactic high molecular...

A novel Ir-catalyzed annulation of imidamides with sulfonyl azides has been developed. 1,2-Disubstituted benzimidazoles could be easily obtained in up to 99% yield for more than 40 examples. The products further streamline the synthesis molecules that are important building blocks organic and drug discovery. This strategy features high regioselectivity, efficiency, good tolerance functional groups, mild reaction conditions.

Vinyl sulfonium salts typically act as an electrophilic Michael acceptor, thus initiating many tandem cyclization reactions. Herein, we disclosed the novel reactivity of vinyl a radical acceptor. Using redox-active ester alkyl precursor, metal-free decarboxylative alkenylation with was realized using eosin Y photocatalyst. This process features broad substrate scope and tolerates range primary, secondary, tertiary carboxylic acids.

Open AccessCCS ChemistryCOMMUNICATION1 May 2022Spirocyclizative Remote Arylcarboxylation of Nonactivated Arenes with CO2 via Visible-Light-Induced Reductive Dearomatization Yuzhen Gao, Hao Wang, Zhuomin Chi, Lei Yang, Chunlin Zhou and Gang Li Gao Key Laboratory Coal to Ethylene Glycol Its Related Technology, Center for Excellence in Molecular Synthesis, Fujian Institute Research on the Structure Matter, University Chinese Academy Sciences, Fuzhou, 350002 , Wang Chi College Chemistry...