Highly regio- and enantioselective rhodium-catalyzed allylic alkylation of 1,3-diketones with racemic secondary alcohols is reported. In the presence a Rh-catalyst derived from Carreira (P, olefin)-ligand TFA as an additive, chiral branched α-allylated could be obtained in good to excellent yields, enantioselectivity (b/l > 19/1, 86–98% ee). The direct utilization allyl electrophiles represents improvement viewpoint atom economy. Both aryl- aliphatic-substituted are suitable substrates...

Abstract A novel rhodium‐catalyzed dearomatization of O‐substituted pyridines to access N‐substituted 2‐pyridones has been developed. computational study suggests a mechanism involving the formation pyridinium ylide followed by an unprecedented 1,4‐acyl migratory rearrangement from O C. Furthermore, chiral dirhodium complexes serve as catalyst for asymmetric transformation with excellent enantioselective control. DFT calculations indicate chirality is transferred axial central stereogenic...

We present here a rhodium-catalyzed asymmetric N-H insertion reaction, which is concerted process revealed by DFT calculations, for the synthesis of novel axially chiral N-arylindoles reaction between indoles and diazonaphthoquinones. The occurs at N1 rather than C2/C3 positions indoles, providing in good yields excellent enantiomeric ratios. Furthermore, this protocol also amenable to N-arylcarbazoles with enantiocontrol.

Abstract Asymmetric carbene insertion reactions represent one of the most important protocols to construct carbon–heteroatom bonds. The use donor–acceptor diazo compounds bearing an ester group is however a prerequisite for achieving high enantioselectivity. Herein, we report chemo‐ and enantioselective formal N−H 2‐pyridones that has been accomplished first time with enynones as donor–donor precursors. DFT calculations indicate unprecedented 1,4‐proton transfer from O C. rhodium catalyst...

By using diazonaphthoquinones and anilines as key reagents through a point-to-axis chiral transfer strategy, the atroposelective synthesis via asymmetric C(sp2 )-H bond insertion reaction of arenes has been realized under rhodium catalysis, providing resulting biaryl atropisomers in moderate to excellent yields with good enantiomeric ratios (up 99:1). Further elaboration indicates this type axially scaffold may have promising potentials developing novel ligands.

A catalyst-controlled selective functionalization of indoles with vinyl diazoacetates has been developed. The use gold catalysts exclusively leads to C3-alkylation products, whereas the highly diastereoselective cyclopropanation reaction is dominant for silver catalysis. Importantly, and vinylcarbenes exhibit carbenic rather than vinylogous reactivity in these transformations.

The unprecedented dearomative migratory rearrangement reactions of 2-oxypyridines with N-sulfonyl-1,2,3-triazoles have been developed under rhodium catalysis, providing a reliable and efficient protocol for accessing N-substituted 2-pyridones. These two distinct rearrangements feature the controllable 1,4-migration carbonate group from O-to-C as well O-to-N 1,6-migration an acyl via α-imino carbene transfer. Moreover, reaction pyridotriazoles delivers products in high efficiency.

The asymmetric synthesis of β2,2 -amino acids remains a formidable challenge in organic synthesis. Here novel organocatalytic enantioselective aminomethylation ketenes with stable and readily available N,O-acetals is reported, providing esters bearing an all-carbon quaternary stereogenic center high enantiomeric ratios catalytic amount chiral phosphoric acid. Typically, this transformation probably proceeds through counter-anion-directed catalysis. As result, concise, practical,...

An enantioselective insertion of a carbene into the Csp2-H bond anisole derivatives has been accomplished using an achiral gold complex and chiral phosphoric acid as catalytic system, providing novel protocol for synthesis α,α-diaryl acetates. Density functional theory calculations reveal reactivity origin enantioselectivity this reaction.

We present here an iridium-catalyzed diastereo- and enantioselective [4 + 1] cycloaddition reaction of hydroxyallyl anilines with sulfoxonium ylides under mild conditions, leading to 3-vinyl indolines in moderate good yields excellent enantioselectivities. Control experiments disclosed a plausible mechanism.

Here we report the first example of iridium-catalyzed asymmetric

An enantioselective synthesis of axially chiral diaryl phenols containing sulfonamide groups has been achieved involving an electrophilic amination 1,1’‐biaryl‐2,6‐diols with N‐sulfonyl quinone diimines, catalyzed by a phosphoric acid. This atroposelective reaction offers modular approach to enantiopure phenols, good excellent yields.

A rhodium-catalyzed reaction of N-hydroxyanilines with diazo compounds to produce α-imino esters was developed. Distinct from the commonly accepted 1,2-H transfer for normal X–H insertion reactions, density functional theory calculations indicate that this transformation proceeds via a novel rebound hydrolysis mechanism. Furthermore, three-component explored synthesize highly functionalized β-lactams in good yields and diastereoselectivities.

An efficient and stereoselective one-pot, two-step tandem α-arylation of glycals from readily available aryl amines via stable diazonium salts has been developed. Moreover, the preparation challenging β-C-glycosyl arenes by anomerization α-C-glycosides using HBF4 is also described. This protocol a broad substrate scope wide functional-group tolerance. It can be used for gram-scale 3-oxo-C-glycosides, which are versatile substrates many biologically important C-glycosides.

A highly enantioselective rhodium-catalyzed allylic dearomatization of β-naphthols with racemic aryl vinyl carbinol is described. In the presence a Rh-catalyst derived from [Rh(C2H4)Cl]2 and chiral (P, olefin)-ligand TFA as an additive, functionalized β-naphthalenone compounds bearing all-carbon-substituted quaternary stereogenic center were obtained in good yields excellent enantioselectivity. addition, this protocol features control prochiral nucleophiles provides first illustration...

An intermolecular enantioselective N-alkylation reaction of 1H-indoles has been developed by cooperative rhodium and chiral phosphoric acid catalyzed N-H bond insertion reaction. N-Alkyl indoles with newly formed stereocenter adjacent to the indole nitrogen atom are produced in good yields (up 95 %) excellent enantioselectivities >99 % ee). Importantly, both α-aryl α-alkyl diazoacetates tolerated, which is extremely rare asymmetric X-H (X=N, O, S et al.) C-H reactions. With this method, only...

An iridium-catalyzed asymmetric [4 + 2] cycloaddition of 1,3,5-triazinanes with 2-(1-hydroxyallyl)anilines/2-(1-hydroxyallyl)phenols has been developed, providing a straightforward and efficient approach to wide range tetrahydroquinazolines in good yields excellent enantioselectivities (up >99% ee). Typically, chiral 1,3-benzoxazines, which are challenging substrates cycloaddition, could be obtained via this protocol.

The development of site-selective and regio- enantioselective reactions substrates with multiple active sites is an important topic remains a substantial challenge in synthetic chemistry. Here, we describe rhodium-catalyzed asymmetric

An unprecedented regio-controllable allylic amination of unactivated dienyl and trienyl alcohols has been developed, providing an efficient approach toward the site-selective formation C1-, C3-, C5-/C7-amination products from sole substrates. Key to this protocol is use secondary amines as reagents, well presence iridium catalyst scandium triflate.

The construction of eight-membered rings is a challenging issue due to unfavorable transannular strain and entropic barriers. We report herein gold-catalyzed formal [4 + 2 2] cycloaddition reaction anthranils with allenamides deliver oxa-bridged heterocycles in accepted yields unique E/Z configuration. Moreover, the asymmetric by using chiral phosphoramidite gold catalyst has also been conducted.

A gold-catalyzed oxy-propargylamination of N-allenamides has been developed by using C-alkynyl N-Boc-acetals as the difunctionalization reagents. Typically, this process features unique proximal addition rather than common distal nucleophilic for gold(I)-activated allenamides. This reaction is atom-economic and provides highly functionalized 1,3-amino alcohol derivatives in good yields with to excellent diastereoselectivities under mild conditions.

A novel B(C₆F₅)₃-catalyzed formal (4+1)-cycloaddition reaction of alkyne-tethered <italic>ortho</italic>-quinone methides with diazoacetates has been well established.

Abstract The Nazarov cyclization is one of the most powerful tools for stereoselective synthesis various cyclopentenone scaffolds. Therefore, developing new classes substrate reaction an important endeavor in synthetic chemistry. Herein, we report enyne diketones, enables diastereo- and enantioselective construction chiral allene cyclopentenones moderate to good yields with enantioselectivities (up 97% ee). Importantly, it a typical example asymmetric cyclopentanones moiety using...

A novel three-component reaction of N,N-disubstituted anilines, diazo compounds, and allylic carbonates has been developed by using a rhodium-palladium dual catalysis, providing an effective protocol for the construction tetrasubstituted esters bearing all-carbon quaternary center as well moiety in one pot.

A copper-catalyzed 1,2-difunctionalization of ynamides has been developed by using readily available N,O-acetals as the bifunctional reagents. Importantly, contrary to initially expected 1,2-oxy-aminomethylation reaction, an unprecedented 1,2-amino-oxymethylation observed. This reaction is atom-economical and tolerates a broad substrate scope, affording difunctionalization products in good yield with unique Z configuration.