Herein, we disclose an efficient cobalt-catalyzed enantioselective C–H activation and annulation of benzamides with alkenes. This transformation is facilitated via the commercially available cobalt(II) catalyst in presence easily prepared chiral salicyl-oxazoline (Salox) ligand, which provides facile access to (R) or (S) enantiomers dihydroisoquinolone derivatives. It noticeable that reaction proceeded efficiently within extremely short time from 10 30 min under mild conditions. A broad...

Abstract Umpolung is an old and important concept in organic chemistry, which significantly expands the chemical space provides unique structures. While, previous research focused on carbonyls or imine derivatives, umpolung reactivity of polarized C–C σ-bonds still needs to explore. Herein, we report reaction bicyclo[1.1.0]butanes (BCBs) with electron-deficient alkenes construct C(sp 3 )-C(sp ) bond at electrophilic position BCBs without any transition-metal catalysis. Specifically, this...

Although breakthroughs in the N-heterocyclic carbene (NHC)-catalyzed inert C–C bond activation strategy have been achieved, understanding role of catalyst as well origin its chemo- and stereoselectivities is still one most challenging questions field organocatalysis. Herein, we propose an NHC NHC·H+ cooperative catalytic model for these kinds reactions perform density functional theory calculations case NHC-catalyzed [4 + 2] annulation reaction conjugated dienal α-aryl ketone. The calculated...

Great success has been achieved in precisely constructing C–C bonds under N-heterocyclic carbene (NHC)/Brønsted acid (BA) cooperative catalysis. However, how NHC and BA co-catalyst accelerate conversions of α,β-unsaturated carbonyls remains unclear. Herein, we have systematically studied several representative NHC/BA catalysis models to help chemists better understand the nature these reactions. The favorable cooperatively catalyzed reactions were identified confirmed by proposed hydrogen...

Transition-metal-catalyzed transformation reactions of epoxides can provide practical C2 synthons in synthetic chemistry. These offer a feasible strategy for catalyst-controlled epoxide divergent transformations. Therefore, finding out the crucial factors controlling chemoselectivity is key to rational design transition-metal-catalyzed conversions with high selectivity. In these studies, we have selected and systematically explored general mechanism both Mn(CO)5–- Co(CO)4–-catalyzed...

The transition metal catalyzed amide bond forming reaction of esters with amines has been developed as an advanced approach for overcoming the shortcomings traditional methods. broad scope substrates in amidations remains a challenge. Here, manganese(I)-catalyzed method direct synthesis amides from various number and is reported unprecedented substrate using low catalyst loading. A wide range aromatic, aliphatic, heterocyclic esters, even fatty acid reacted diverse primary aryl amines, alkyl...

A DFT study on competing mechanisms of NHC-catalyzed reactions enals with 2-aminoacrylates has been performed for the first time.

The possible mechanism and stereoselectivity of the NHC-catalyzed ring expansion reaction oxaziridines have been theoretically studied for first time.

Hydroboration reactions of carboxylic acids using sodium aminodiboranate (NaNH2[BH3]2, NaADBH) to form primary alcohols were systematically investigated, and the reduction mechanism was elucidated experimentally computationally. The transfer hydride ions from B atoms C atoms, key step in mechanism, theoretically illustrated supported by experimental results. intermediates NH2B2H5, PhCH═CHCOOBH2NH2BH3–, PhCH═CHCH2OBO, byproducts BH4–, NH2BH2, NH2BH3– identified characterized 11B 1H NMR....

N-Heterocyclic carbene (NHC) catalyzed desymmetrizing reactions of olefins have rapidly developed in recent years; however, the origins chemo- and stereoselectivities these remain poorly understood. Herein, we propose a mechanistic map for to predict how are controlled by different active intermediates (i.e., Breslow acylazolium intermediates). Remarkably, our findings contradict previous proposition that product structures determined transformation between pair isomers.

The mechanism and origin of selectivities NHC-catalyzed arylation azonaphthalenes with α-chloroaldehydes have been theoretically studied for the first time.

We here described a method to synthesize α-keto amides from simple sulfoxonium ylides and secondary amines under the catalysis of copper. This transformation involved very clean catalytic system, substrates could be extended aryl, heteroaryl, tert-butyl give diversified with good yields. Additionally, mechanistic studies indicated that α-carbonyl aldehyde might key intermediate in reaction system.

N-Heterocyclic carbene and Lewis acid cooperatively catalyzed oxidative [3 + 3] annulation reactions of 1,3-dicarbonyl compounds have been systematically studied in theory.

A general mechanism for N-heterocyclic carbene-catalyzed decarboxylation reactions has been studied using DFT calculations.

An efficient synthetic method for KB 3 H 8 has been developed and general mechanisms of formation the B − anion have elucidated.

Here, we report a theoretical investigation of the reactivity and chemoselectivity carbene-enabled ether activation.

Dearomatization reactions have recently emerged as a powerful tool for the rapid buildup of molecular complexity. Here, an unparalleled thermal dearomatization [4+2] cycloaddition reaction between benzene derivatives and 2H-phosphindole tungsten complex was reported. The unique reactivity in situ-generated toward revealed by density functional theory calculations. We thus provide new insights into nonactivated arenes pave way manipulation further applications.

Abstract The proportion of geometrical hydroperoxide isomers generated by aerobic oxidation methyl linoleate (18∶2 Me) in either aqueous emulsion consisting Tris‐HCl buffer (pH 7.4) or a homogeneous dichloromethane solution was determined to understand the mechanism lipid different reaction systems. Four were after 18∶2 Me dichloromethane: 13‐hydroperoxy‐ cis ‐9, trans ‐11‐octadecadienoate, 9‐hydroperoxy‐ ‐10, ‐12‐octadecadienoate, and ‐12‐octadecadienoate ratios 1∶4∶1∶4, respectively....

Due to the ubiquity of carbonyl compounds and abundance nickel on earth, nickel-catalyzed decarbonylation has garnered increasing attention in recent years. This type reaction seen significant developments various aspects; however, certain challenges concerning reactivity, selectivity, transformation efficiency remain pressing demand urgent resolution. In this study, we employed DFT calculations investigate mechanism reactions involving lactones, as well effects phosphine ligands....