Search

Transition-metal-catalyzed directed C–H functionalization with various carbene precursors has been widely employed for constructing a wide range of complex and diverse active molecules through metal carbene migratory insertion processes. Among various carbene precursors, iodonium ylides serve as a novel and emerging carbene precursor with features including easy accessibility, thermal stability and high activity, which have attracted great attention from organic chemists and have achieved tremendous success in organic transformation. In this review, recent progress on the application of iodonium ylides with multifunctional coupling characteristics in C–H bond activation reactions is summarized, and the potential of iodonium ylides is discussed. [ABSTRACT FROM AUTHOR]

A highly efficient, diastereoselective strategy for the synthesis of aryl‐substituted spiro‐epoxyoxindole derivatives by a Darzens‐type reaction of α‐chlorooxindoles with aryl aldehydes in the presence of bases under solvent‐free grinding conditions has been developed. The process features with easy work‐up, mild reaction condition, high to excellent diastereoselectivitie and yields as well as environmental compatibility. [ABSTRACT FROM AUTHOR]

An efficient Rh(III)‐catalyzed C−H activation and annulation cascade of primary benzylamines with readily accessible α‐Cl ketones was developed. This transformation provides an easy and robust approach to diverse isoquinolines under air with broad functional group tolerance. [ABSTRACT FROM AUTHOR]

A new P(OEt)3-mediated formal S–H bond-insertion reaction of isatins into thiols for the synthesis of valuable 3-sulfenylation oxindoles has been developed. This approach takes advantage of the unique reactivity of Kukhtin–Ramirez adducts to allow direct reductive S–H functionalization with commercially available and bench-stable starting materials. [ABSTRACT FROM AUTHOR]

An efficient stereoselective assembly strategy for the construction of pyrrolidin-2,3′-oxindole cis -fused phosphadihydrocoumarins was established. The process involves the condensation of O-vinylphosphonylated salicylaldehydes and 3-amino oxindoles followed by intermolecular cycloaddition with high diastereoselectivity and atom economy. [ABSTRACT FROM AUTHOR]

Enantiomerically pure organoperoxides serve as valuable precursors in organic transformations. Herein, we present the first examples of unspecific peroxygenase catalyzed kinetic resolution of racemic organoperoxides through asymmetric reduction. Through meticulous investigation of the reaction conditions, it is shown that the unspecific peroxygenase from Agrocybe aegerita (AaeUPO) exhibits robust catalytic activity in the kinetic resolution reactions of the model substrate with turnover numbers up to 60000 and turnover frequency of 5.6 s -1 . Various aralkyl organoperoxides were successfully resolved by AaeUPO, achieving excellent enantioselectivities (e.g., up to 99 % ee for the (S)-organoperoxide products). Additionally, we screened commercial peroxygenase variants to obtain the organoperoxides with complementary chirality, with one mutant yielding the (R)-products. While unspecific peroxygenases have been extensively demonstrated as a powerful oxidative catalysts, this study highlights their usefulness in catalyzing the reduction of organoperoxides and providing versatile chiral synthons., (© 2024 Wiley-VCH GmbH.)

A metal-free direct sulfenylation of phenol and arylamine derivatives with various heterocyclic thiols and thiones using a cross dehydrogenative coupling protocol in water at room temperature has been developed. In addition, this chemical method has several advantages including odorless sulfur sources, good functional group tolerance, green solvent, and mild conditions, making it more environmentally friendly.