The oxidant directs: A mild, practical, efficient, and regioselective Ru-catalyzed isoquinolone synthesis with a broad substrate scope was reported (see scheme). In this redox neutral process, the aromatic CH bond functionalization can be performed at room temperature without using any external oxidant. mechanism of reaction probed, it found that activation is turnover-limiting step. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents...

Ruthenium-catalyzed oxidative C-H bond olefination of N-methoxybenzamides using an oxidizing directing group with a broad substrate scope is reported. The reactions acrylates in MeOH and styrene (or norbornadiene) CF(3)CH(2)OH afforded two types products.

The cascade oxidative annulation reactions of benzoylacetonitrile with internal alkynes proceed efficiently in the presence a rhodium catalyst and copper oxidant to give substituted naphtho[1,8-bc]pyrans by sequential cleavage C(sp(2))-H/C(sp(3))-H C(sp(2))-H/O-H bonds. These are highly regioselective unsymmetrical alkynes. Experiments reveal that first-step reaction proceeds bonds alkynes, leading 1-naphthols as intermediate products. Subsequently, react bonds, affording 1:2 coupling...

A highly efficient binary system consisting of polyethylene glycol and an amidine or guanidine superbase was developed for CO2 absorption, leading to the activation molecules, thus direct conversion captured value-added chemicals fuels successfully performed avoid desorption.

Go go Grignard! The first highly regioselective, cobalt-catalyzed CH transformation of benzo[h]quinoline and phenylpyridine derivatives with Grignard reagents at room temperature has been achieved (see scheme). Both aryl alkyl showed significant reactivity. Detailed facts importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by the authors. Please note: publisher is responsible...

Abstract The alkenylation reactions of 8‐methylquinolines with alkynes, catalyzed by [{Cp*RhCl 2 } ], proceeds efficiently to give 8‐allylquinolines in good yields C(sp 3 )H bond activation. These are highly regio‐ and stereoselective. A catalytically competent five‐membered rhodacycle has been structurally characterized, thus revealing a key intermediate the catalytic cycle.

Rh(<sc>iii</sc>)-catalyzed synthesis of 1-aminoindole derivatives from 2-acetyl-1-arylhydrazines and diazo compounds has been developed, through tandem C–H activation, cyclization condensation.

Selective oxidation of sulfides was successfully performed by employing oxone (2KHSO5·KHSO4·K2SO4) as oxidant without utilization any catalyst/additive under mild reaction conditions. Notably, the can be controlled chosen solvent. When ethanol used solvent, sulfoxides were obtained in excellent yield; almost exclusively gave sulfone water. Furthermore, this protocol worked well for various to corresponding or sulfones

An efficient and regioselective ruthenium-catalyzed oxidative annulation of enamides with alkynes via the cleavage C(sp2)–H/N–H bonds is reported. The reactions can afford N-acetyl substituted or N-unsubstituted pyrroles by altering reaction conditions slightly.

A novel synthetic approach toward benzo[a]carbazoles or 6-amino containing an unprotected NH unit through Rh(iii)-catalyzed cascade reactions of 2-arylindoles 2-arylindole-3-carbonitriles with α-diazo carbonyl compounds has been established. To our knowledge, this is the first example in which indole used as a directing group for intramolecular C(sp2)-H bond functionalization to give benzo[a]carbazole derivatives. Notably, method features easily obtainable substrates, good functional...

Abstract A highly chem‐ and regioselective synthesis of diversely substituted benzo[ a ]carbazoles indolo[2,1‐ ]‐isoquinolines through Rh(III)‐catalyzed cascade reactions 2‐arylindoles with sulfoxonium ylides is presented. To be specific, treatment 2‐arylindoles, 2‐arylindole‐3‐carbaldehydes, 2‐arylindole‐3‐carbonitriles or 2‐aryl‐3‐methylindoles under the catalysis Rh(III) led to selective formation 6‐aryl/alkyl ]carbazoles, 5‐acylbenzo[ 6‐amino‐5‐acylbenzo[ 12‐methylindolo[2,1‐...

Radical borylation using N-heterocyclic carbene (NHC)-BH3 complexes as boryl radical precursors has emerged an important synthetic tool for organoboron assembly. However, the majority of reported methods are limited to reaction modes involving carbo- and/or hydroboration specific alkenes and alkynes. Moreover, generation NHC-boryl radicals relies principally on hydrogen atom abstraction with aid initiators. A distinct method is reported, well pathways enabled by photoredox catalysis....

The rhodium(III)-catalyzed intermolecular C7-thiolation and selenation of indolines with disulfides diselenides were developed. This protocol relies on the use a removable pyrimidyl directing group to access valuable C-7 functionalized indoline scaffolds ample substrate scope broad functional tolerance.

Abstract The mechanism of [{RuCl 2 ( p ‐cymene)} ]‐catalyzed oxidative annulations isoquinolones with alkynes was investigated in detail. first step is an acetate‐assisted CH bond activation process to form cyclometalated compounds. Subsequent mono‐alkyne insertion the RuC bonds compounds then takes place. Finally, coupling CN occurs afford Ru 0 sandwich complexes that undergo oxidation regenerate catalytically active II complex copper oxidant and release desired dibenzo[ a , g...

A dehydrogenative annulation of 2-arylindazoles with maleimides for the switchable synthesis indazolo[2,3-a]pyrrolo[3,4-c]quinolinones or spiroindolo[1,2-b]indazole-11,3′-pyrrolidinones is presented. Mechanistically, formation title compounds involves a Rh(III)-catalyzed C–H metalation 2-arylindazole, followed by maleimide insertion and intramolecular cyclization. Interestingly, selectivity to form fused spiro could be switched resorting different additives. The notable features this...

Be economic with your atoms! An efficient Rh-catalyzed oxidative olefination of indoles and pyrroles broad substrate scope tolerance is reported (see scheme). The catalytic reaction proceeds excellent regio- stereoselectivity. directing group N,N-dimethylcarbamoyl was crucial for the could be removed easily. Mizoroki–Heck one most important metal-catalyzed cross-coupling reactions formation a CC bond from CX bond.1 However, direct CH transformations allow use less expensive more readily...

A Cp*Co(III)-catalyzed C-H bond functionalization of a range arenes by employing sulfoxonium ylides as carbene precursors instead diazo compounds and other has been established. This reaction is highly efficient without any additive, possesses high step atom economies, tolerates functional groups.

A simple method for the efficient synthesis of highly substituted pyrido[1,2-a]quinolinium- and quinolizino[3,4,5,6-ija]quinolinium-based polyheteroaromatic compounds via rhodium(III)-catalyzed multiple C–H activation annulation reactions has been developed. Moreover, some quinolizino[3,4,5,6-ija]quinolinium salts exhibit intense fluorescence have potential application in optoelectronic materials.

Carboxyl group is one of the most widely used groups in organic synthesis. Herein, an efficient copper-catalyzed carboxylation aryl thianthrenium salts with carbon dioxide (CO2 ) at room temperature has been developed. The reaction employs low loading cuprous chloride catalyst under 1 atm CO2 and exhibits good functional tolerance. In combination C-H thianthrenation aromatic hydrocarbons, this work provides method for site-selective hydrocarbons. It may serve as a significant late-stage tool...

The development of functionally distinct catalysts for enantioselective synthesis is a prominent yet challenging goal synthetic chemistry. In this work, we report family chiral N-heterocyclic carbene (NHC)-ligated boryl radicals as that enable catalytic asymmetric radical cycloisomerization reactions. can be generated from easily prepared NHC-borane complexes, and the broad availability NHC component provides substantial benefits stereochemical control. Mechanistic studies support cycle...

Presented herein is a solvent-dependent selective synthesis of CF3-tethered indazole derivatives via the cascade reactions 1-arylpyrazolidinones with trifluoromethyl ynones. Mechanistically, formation title products involves N–H/C–H/C–N/C–C bond cleavage along pyrazole ring and pyrazolidinone opening. For scaffold, 1-phenylpyrazolidinone acts as C2N2 synthon, while ynone serves C1 synthon. Meanwhile, also an enol unit to facilitate opening provide trifluoropropenoxy fragment alkynyl triple...

Presented herein is a novel synthesis of pharmaceutically privileged spiroindoline derivatives via cascade reactions N-methyl-N-nitrosoanilines with diazo homophthalimides. A group mechanistic studies disclosed that the formation product involves an unusual reaction mode N-methyl-N-nitrosoaniline featuring initial C(sp2)–H bond activation/alkylation followed by C(sp3)–H activation/spiroannulation. To our knowledge, this first example in which acts as C3N1 synthon to accomplish formal [4+1]...

Abstract Pyridine motifs are widespread pharmacophores in many drugs. Installing various substituents through pyridine C−H bond functionalization is significant for new drug design and discovery. Developments of late‐stage reactions enrich the strategies selective pyridines. However, carboxylation pyridines a long‐standing challenge, especially selectively with CO 2 on motifs. Herein, we describe practical method C4−H via one‐pot phosphination copper‐catalyzed resulted phosphonium salts ....

Readily available iron compounds were found to be active catalysts for the selective oxidation of sulfide sulfoxide with molecular oxygen as oxidant in polyethylene glycol (PEG). As an indispensable component, PEG had a great promotive effect on reaction. Notably, high conversion (>99%) along excellent chemo-selectivity up 94% could attained by using Fe(acac)2 catalyst at 100 °C. This methodology was proved applicable transformation various aromatic and aliphatic sulfides into corresponding...

An efficient ruthenium-catalyzed oxidative coupling of indoles and pyrroles with various alkenes at the C2-position assisted by employing N,N-dimethylcarbamoyl moiety as a directing group is reported. The catalytic reaction proceeds in an excellent regio- stereoselective manner.