All in a sequence: An organocatalyzed Morita–Baylis–Hillman (MBH)/bromination/[3+2] annulation sequence for highly stereoselective syntheses of bis(spirooxindole)s featuring adjacent spiro-stereocenters is described. The key step an unprecedented catalytic asymmetric [3+2] isatin-derived MBH adducts, containing tetrasubstituted alkene moiety, with isatins.

We report a highly enantioselective Morita-Baylis-Hillman (MBH) reaction of isatins and acrolein to provide enantiomerically enriched 3-substituted 3-hydroxyoxindoles, which could serve as valuable synthetic building blocks. This is also the first time that ketone has been used electrophile nucleophile in catalytic asymmetric MBH reaction. Hatakeyama's catalyst, β-isocupreidine (1), turned out be powerful catalyst for this transformation.

Phosphoranes 2 are identified as a class of effective Lewis bases to activate chiral (salen)AlCl complex 1 enhance its electrophilicity. Accordingly, three-component catalyst system consisting 1, phosphorane 2e, and Ph3PO is developed powerful tool for asymmetric ketone cyanosilylation. In particular, an unprecedented highly enantioselective cyanosilylation linear aliphatic ketones achieved. A tandem Wittig-cyanosilylation sequence starting from 2a enals 10 further achieved, which internally...

Highly enantioselective CuAAC reactions for the synthesis of versatile <italic>P</italic>-chiral phosphorus synthons featuring a ethynyl group were developed.

A chiral thulium(III)-catalyzed sulfur-conjugation addition reaction of dialkynylphosphine oxides to construct P-stereogenic centers has been developed. Dialkynylphosphine bearing aryl, alkyl, alkenyl substitution at the alkyne terminus position were tolerated under conditions. The corresponding P,S-containing compounds obtained in moderate good yields (up 92% yield) with high Z/E ratios and enantioselectivities >95/5 97% ee), which could be transformed into versatile optically active...

The structural elucidation of chiral rare-earth-based catalysts in asymmetric reactions holds significant importance as it is crucial for comprehending their operational mechanisms and broadening applications the realm synthesis. Herein, a LaIII/(L3-RaMe3)2 complex was identified to be more active enantioselective than LaIII/L3-RaMe3 formal substitution racemic 3-bromo-3-substituted oxindoles with TMSCN. experimental studies theoretical calculations disclosed that partial dissociation...

Organic azides play important roles in synthetic chemistry, chemical biology, drug discovery, and material science. Azido-functionalization of alkenes is one the most efficient procedures for rapid introduction azide group into organic compounds. But only a few examples have been documented catalytic asymmetric version azidation alkenes. Herein, we report an unprecedented highly diastereo- enantioselective bromoazidation α,β-unsaturated ketones catalyzed by chiral N,N′-dioxide/Fe(OTf)2...

Enantioselective photoreduction of ketones with hydrocarbons is promising for the straightforward construction chiral tertiary alcohols. But it generally promoted by ultraviolet light via ketyl radical–alkyl radical coupling, which suffers from a competitive charge-transfer process and self/cross coupling reactions. An appropriate selection catalyst that can alter reaction pathway deliver spatial required. Accordingly, we disclosed combined system involving Er(III)-based Lewis acid...

A highly enantioselective tandem Pudovik addition/[1,2]-phospha-Brook rearrangement of α-alkynylketoamides with diarylphosphine oxides was achieved a N,N'-dioxide/ScIII complex as the catalyst. This protocol features broad substrate scope, high regio- and enantioselectivity, good functional-group compatibility, providing straightforward route to various trisubstituted allenes diarylphosphinate functionality in yields enantioselectivities (up 97 % yield, 96 ee). Control experiments...

A 2-alkenoylpyridine-bound N,N'-dioxide-TbIII complex has been found to absorb visible light reach the excited state, leading direct visible-light-excited catalytic enantioselective [2+2] cycloaddition of 2-alkenoylpyridines various alkenes in absence an additional photosensitizer. Diverse enantioenriched cyclobutanes were successfully obtained (yields up 70 %, >19:1 d.r., 92 % ee). The new chiral terbium(III) features a bathochromic shift, lower excitation energy, and facile intersystem...

The enantioselective construction of quaternary carbon centers is a marked challenge in asymmetric catalysis research. It extremely difficult when chiral catalyst can not distinguish the facial selectivity substrate through bond interactions. Here we realized an Michael reaction silyl ketene imines to 1-acrylpyrazoles using N,N′-dioxide–Co(II) complex. protocol highly efficient for nitrile-, aryl-, and dialkyl-bearing has been successful applied divergent synthesis pharmaceuticals natural...

Optically enriched Hantzsch dihydropyridines bearing different ester groups were obtained through the asymmetric catalytic cascade reaction between 3-amino-2-butenoates and (Z)-2-arylidene-3-oxobutanoates. The N,N′-dioxide/NiII or NdIII complex catalysts disclosed to be efficient, furnishing a variety of products, including drugs like nitrendipine, nimodipine, felodipine, in high yields (up 99% yield) with excellent enantioselectivities ee). Two enantiomers products can readily via exchange...

Asymmetric tandem Heck and carbonylation reactions provide an efficient route to synthesize biologically important chiral cyclic compounds with a carbonyl group have attracted increasing research interests. However, this type of reaction relies on the initiation from oxidative addition aryl halides or pseudo halides, resulting in low atomic economy reaction. In addition, protocol has not adequately demonstrated reactivity generality heteroarene halides. Meanwhile, asymmetric Wacker-type...

A metal-free tandem Friedel-Crafts/lactonization reaction to 3,3-diaryl or 3-alkyl-3-aryl benzofuranones catalyzed by HClO(4) was reported. variety of tertiary α-hydroxy acid esters could readily react with substituted phenols afford the desired products in rich diversity. The synthetic utility demonstrated synthesis polycyclic compounds. (1)H NMR studies supported that this proceeded via sequence.

Immer der Reihe nach: Eine organokatalytische Sequenz aus Morita-Baylis-Hillman(MBH)-Reaktion, Bromierung und [3+2]-Ringschluss führt hoch stereoselektiv zu Bis(spirooxindolen) mit benachbarten Spiro-Stereozentren. Der Schlüsselschritt dabei ist katalytische asymmetrische zwischen von Isatinen abgeleiteten MBH-Addukten, die eine vierfach substituierte Doppelbindung tragen, weiteren Isatinderivaten. As a service to our authors and readers, this journal provides supporting information supplied...

Abstract A variety of enantioenriched indole derivatives substituted in the benzene ring were synthesised via an organocatalytic asymmetric aza‐Friedel‐Crafts reaction pyrazolinone ketimines with hydroxyindoles. This was also applicabled to electron‐rich phenols, yielding desired products high yields (up 99%) and excellent stereo‐selectivities (91–99% ee). Moreover, this method presents its potential synthesis structurally novel indole‐pyrazolinone conjugate derivatives. magnified image

A palladium-catalyzed asymmetric C-C bond activation/carbonylation of cyclobutanones with CO has been developed. This reaction provided an efficient method for the synthesis chiral indanones bearing a quaternary carbon stereocenter in good yields excellent enantiomeric ratio, exhibiting functional group tolerance. Transformations products to 3,4-dihydroquinolin-2(1H)-one and 1H-indene further demonstrated versatility this reaction.

Olefin cross-metathesis is an effective tool for the functionalization of biodegradable aliphatic polyesters through both pre- and post-polymerization β-heptenolactone (βHL). Ring-opening polymerization βHL accesses homopolymers novel copolymers, producing strong gradient copolymers with lactide. A total 15 different alkene cross-partners ranging from type I to III olefins are readily incorporated produce a range functionalities, altering thermal chemical properties resulting polymers....

A novel oxy-aminomethylation reaction of diazo compounds has been developed, providing the α-hydroxy-β2-amino acid derivatives with quaternary carbon centers in moderate to excellent yields. Importantly, readily available N, O-acetals have employed as efficient bifunctionalization reagents react copper carbene intermediates, leading concurrent incorporation an alkoxy and iminium group into one molecule. Moreover, a water-involved three-component occurs deliver free-hydroxy amino derivatives.

An efficient synthesis of chiral benzannulated spiroketals via catalytic asymmetric [3 + 2] cycloaddition exocyclic enol ethers with p-quinones was achieved. The transformation enabled by a N,N′-dioxides/TmIII complex as the Lewis acid catalyst and afforded series enantiomerically enriched spiroketal derivatives in good yields (up to 99%) enantioselectivities 98% ee). Topographic steric maps distribution buried volumes catalysts Cavallo's SambVca 2 tool were used elucidate enantioinduction...

A practical and environmentally benign synthesis of poly-substituted tetrahydropyrimidines <italic>via</italic> formal [3+3]-annulation imines 1,3,5-hexahydro-1,3,5-triazines under catalyst-free conditions has been developed.

The α-methylene-γ-butyrolactone motif is a widely encountered unit in many natural products and pharmaceutical compounds. Herein, practical efficient synthesis of α-methylene-γ-butyrolactones from readily available allylic boronates benzaldehyde derivatives was developed with chiral N,N'-dioxide/AlIII complex as the catalyst. key success this transformation kinetic resolution allylboration intermediate via asymmetric lactonization. This protocol enabled to assemble all four stereoisomers...