Something constructive: The title reaction involving 3-hydroxyoxindoles gives 3,3′-disubstituted oxindoles with concomitant generation of an all-carbon quaternary stereogenic center in high yield and excellent enantioselectivity. This enabled the enantioselective construction hexahydropyrroloindole skeletons first catalytic total synthesis (+)-folicanthine. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not...

Highly enantioselective [3+3] and [3+4] annulations of isatin-derived enals with ethynylethylene carbonates ethynyl benzoxazinanones are enabled by NHC/cooper cooperative catalysis, leading to a big library spirooxindole derivatives in high structural diversity enantioselectivity (up 99 % ee). Both reactions represent nicely synergistic integration NHC copper which both catalysts activate the substrates chiral perfectly controls stereochemistry.

Abstract An asymmetric catalytic decarboxylative [4+2] annulation of 4‐ethynyl dihydrobenzooxazinones and carboxylic acids has been established by cooperative copper nucleophilic Lewis base catalysis. A C1 ammonium enolate copper–allenylidene complex, each catalytically generated from different substrates, underwent a cascade propargylation lactamization process to yield optically active 3,4‐dihydroquinolin‐2‐one derivatives with excellent levels stereoselectivity (up 99 % ee , 95:5 d.r.).

Spirooxindoles have emerged as promising architectures for engineering biologically active compounds. The diastereodivergent construction of unique scaffolds this type with full control continuous chiral centers including an all-carbon quaternary stereogenic center is yet to be developed. Here, we report unprecedented desymmetric [3 + 3] annulation oxabicyclic alkenes enals enabled by N-heterocyclic carbene (NHC)/Rh cooperative catalysis, leading a series enantiomerically enriched...

The exploitation of carbon dioxide (CO2) as a sustainable, plentiful, and harmless C1 source for the catalytic synthesis enantioenriched carboxylic acids has long been acknowledged pivotal task in synthetic chemistry. Herein, we present current-driven nickel-catalyzed reductive carboxylation reaction with CO2 fixation, facilitating formation C(sp3)–C(sp2) bonds by circumventing handling moisture-sensitive organometallic reagents. This electroreductive protocol serves practical platform,...

A highly enantioselective CH-activation-based oxidative coupling reaction of 3-arylmethylindole derivatives with dibenzyl malonate by using chiral Lewis acid bonded nucleophiles provided an approach to indole (see scheme; DDQ=2,3-dichloro-5,6-dicyano-1,4-benzoquinone, OTf=trifluoromethanesulfonate). Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted the authors....

Organocatalytic enantioselective Biginelli and Biginelli-like reactions by chiral phosphoric acids derived from 3,3′-disubstituted binaphthols have been investigated. The size of 3,3′-substituents the catalysts is able to control stereochemistry reaction. By tuning 3,3′-disubstituents acids, reaction can be reversed. This organocatalytic Brønsted 12b 13 applicable a wide range aldehydes various β-keto esters, providing highly method access DHPMs. 3,3′-Di(triphenylsilyl) binaphthol-derived...

12-Step program: The combined use of cinchona alkaloid based amine and chiral phosphoric acid enabled the asymmetric alkylation reaction 3-hydroxyoxindoles with aldehydes to give 3,3′-disubstituted oxindoles in excellent enantioselectivities, which allows for enantioselective total synthesis (+)-gliocladin C 12 steps from 3-hydroxyoxindole 19 % overall yield (see scheme; PMB=para-methoxybenzyl).

Abstract Indole and its structural analogues have been frequently found in numerous alkaloids, pharmaceutical products related materials. The enantioselective construction of these structures allows efficient total synthesis optically pure indole hence has received worldwide interest. In the past decade, asymmetric organocatalysis recognized as one most powerful strategies to create chiral molecules with high levels stereoselectivity. particular, organocatalytic cascade reactions often occur...

An enantioselective α-amination of esters by a Lewis base/copper(I) cooperative catalysis strategy has been developed. The transient chiral C1-ammonium enolate generated from pentafluorophenyl ester and nucleophilic base is nicely compatible with the copper intermediate formed N,N-di-t-butyldiaziridinone Cu(I) to allow for high levels stereochemical control. catalytic reaction leads diverse set highly enantioenriched hydantoins in good yields excellent enantioselectivities (90–99% ee).

Highly enantioselective [4 + 2] cyclizations of azadienes with in situ generated ketenes were developed through sequential visible-light photoactivation/isothiourea catalysis, which offers a novel approach for the creation all-carbon quaternary stereocenters disubstituted C1-ammonium enolates. The visible-light-induced sustained release reactive ketene species Wolff rearrangement α-diazoketones is crucial achieving high levels chemical efficiency and stereoinduction.

Abstract Catalytic kinetic resolution (KR) and dynamic asymmetric transformation (DyKAT) are alternative complementary avenues to access chiral stereoisomers of both starting materials reaction products. The development highly efficient catalytic systems for kinetically controlled processes has therefore been one the linchpins in synthesis. N‐heterocyclic carbene (NHC)/copper cooperative catalysis enabled KR DyKAT racemic N ‐tosylaziridines by [3+3] annulation with isatin‐derived enals,...

Abstract Despite that asymmetric stereodivergent synthesis has experienced great success to provide unusual processes for the creation of chirality complexity, concepts appliable catalysis are still limited. The dependence on capacity each catalyst precisely control reactive site planar in region poses unparalleled constraints this field. Here, we first demonstrate chiral Cu-allenylidene species can participate propargylic alkylation enals, concert with N-heterocyclic carbenes (NHCs). Thus,...

The feasibility of cooperative catalysis between chiral N-heterocyclic carbenes and nickel in asymmetric reactions has been demonstrated convincingly. high efficiency this catalytic system enables the allylic alkylation isatin-derived enals with carbonates [3+3] annulation racemic vinyl epoxides to provide straightforward access highly enantioenriched 3,3'-disubstituted oxindoles. great practicality method organic synthesis showcased by facile product modification enantioselective key...

ADVERTISEMENT RETURN TO ISSUEPREVLetterNEXTHighly Enantioselective Catalytic 1,3-Dipolar Cycloaddition Involving 2,3-Allenoate DipolarophilesJie Yu, Long He, Xiao-Hua Chen, Jin Song, Wei-Jie and Liu-Zhu Gong*View Author Information Hefei National Laboratory for Physical Sciences at the Microscale Department of Chemistry, University Science Technology China, Hefei, 230026, China[email protected]Cite this: Org. Lett. 2009, 11, 21, 4946–4949Publication Date (Web):October 8, 2009Publication...

Silver-standard selectivity! The first highly enantioselective formal [3+2] cycloaddition reaction of isocyanoesters with 2-oxobutenoate esters catalyzed by a chiral silver complex proceeded readily under the catalysis multifunctional in high yields and enantiometric excess (ee) values up to 98 % (see scheme). Detailed facts importance specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted...

The first asymmetric catalytic biomimetic three-component 1,3-dipolar cycloaddition of α-keto esters and benzylamine with electron-deficient olefins, inspired by the transamination acids involving pyridoxal phosphate (PLP)-dependent enzymes in biological systems, giving several families structurally diverse pyrrolidine derivatives high yields excellent enantioselectivities (up to 99% ee) under mild conditions is described.

Konstruktiver Beitrag: Die Titelreaktion unter Beteiligung von 3-Hydroxyoxindolen liefert Oxindole mit einem rein C-substituierten quartären stereogenen Zentrum in hoher Ausbeute und exzellenter Enantioselektivität. Reaktion ermöglichte die enantioselektive Synthese Hexahydropyrroloindol-Gerüsten erste katalytische Totalsynthese (+)-Folicanthin.

The first catalytic asymmetric decarboxylative [3 + 2] cycloaddition reaction of ethynylethylene carbonates with malononitrile has been developed successfully by an organo/copper cooperative system. This strategy led to a series optically active polysubstituted dihydrofurans in good yields high levels enantioselectivities (up 99% yield, 97% ee). presence the terminal alkynyl and cyano group dihydrofuran products provides wide scope for further structural transformations. More importantly,...

Abstract A general strategy for the design of asymmetric cascade reactions using readily available halides and carbon monoxide (CO) as substrates is developed. The key catalytic generation C1‐ammonium enolates subsequent through combination palladium‐catalyzed carbonylation chiral Lewis base catalysis. Utilizing this strategy, we have established formal [1+1+4] [1+1+2] to afford dihydropyridones β‐lactams with high yields enantio‐ diastereoselectivities.

The creation of full stereoisomers an organic compound comprising multiple contiguous stereocenters with simultaneous control over both relative and absolute configurations remains a significant challenge in synthetic chemistry. Using cooperative catalysis strategy, we established N-heterocyclic carbene/nickel-catalyzed enantio- diastereodivergent propargylation reaction to access 3,3'-disubstituted oxindoles, enabling the incorporation internal alkyne functionality introduction single...

Abstract An asymmetric catalytic decarboxylative [4+2] annulation of 4‐ethynyl dihydrobenzooxazinones and carboxylic acids has been established by cooperative copper nucleophilic Lewis base catalysis. A C1 ammonium enolate copper–allenylidene complex, each catalytically generated from different substrates, underwent a cascade propargylation lactamization process to yield optically active 3,4‐dihydroquinolin‐2‐one derivatives with excellent levels stereoselectivity (up 99 % ee , 95:5 d.r.).

The first catalytic enantioselective decarboxylative propargylation/hydroamination reaction of ethynyl benzoxazinanones with malononitriles enabled by organo/copper cooperative catalysis was established. Various 3-indolin-malononitrile derivatives, displaying a high tolerance for functional groups, could be obtained in good yields levels enantioselectivity (up to 85% yield, 96:4 er). More importantly, this organo/metal system will provide powerful synthetic strategy new development.

A fluorinative Beckmann fragmentation of α-oximinoamides was devised to provide synthetically useful carbamoyl fluorides. High selectivity for over a potentially competing rearrangement observed. This protocol has distinct mechanism and thus different substrate scope compared with other synthetic methods. α-Oximinoamides derived from the readily available secondary amines, lactams, or isatins were converted into structurally diverse

Chiral γ-lactam-containing skeletons are important motifs in bioactive natural products, pharmaceuticals, and molecules. Herein, we report a general modular platform to access chiral γ-lactam compounds via an ITU/Ir cooperatively catalyzed [3 + 2] asymmetric annulation reaction of vinyl aziridines with pentafluorophenyl esters. Through the Lewis base transition metal cooperative catalytic regime, broad range optically active γ-lactams were generated good yields (up 92%) high induction 98%...