Transition-Metal-Catalyzed Directing Group Assisted (Hetero)aryl C-H Functionalization: Construction of C-C/C-Heteroatom Bonds.

Transition-metal-catalyzed C-H functionalization is one of the fascinating scientific fronts in organic synthesis for the formation of conjugated arenes and has emerged as a benchmark to revolutionize the synthetic enterprise since past decades. In this realm, chelation-guided functionalization of C-H bonds using an exogenous directing group has received considerable attention recently for the expedient regioselective construction of C-C and C-heteroatom bonds as an efficient and sustainable alternative. This article outlines our contribution towards a wide variety of transformations that have been achieved by the directed C-H functionalization through the fine tuning of catalytic systems.

The transition-metal-catalyzed stereoselective ring-expansion of vinylaziridines and vinyloxiranes.

The transition-metal-aided stereoselective construction of sp3-carbon-rich heterocyclic scaffolds using strained-ring systems has received considerable attention in recent years due to the prominent presence of these scaffolds in myriad natural products, bioactive molecules, and pharmaceutical components. In this area, the catalytic ring-enlargement of vinylaziridines and vinyloxiranes plays a predominant role when synthesizing high sp3-content biorelevant heterocyclic compounds. This article aims to portray recent advancements in the ring-expansion of vinylaziridines and vinyloxiranes for accessing densely functionalized stereoselective heterocycles that have been developed over the past five years, with an emphasis on the substrate scopes and mechanistic insights into the key methodologies, and it is arranged based on the transition metals used and the ring sizes of the heterocyclic scaffolds.

Oncocytic adrenal cortical adenoma: a benign lesion mimicking malignancy.

Adrenocortical tumours are rare in children and account for only 0.3%-0.4% of all neoplasms in childhood. They present with variable signs and symptoms, depending on the type of hormonal hypersecretion. The majority of the adrenocortical tumours in children are functional (90%) and malignant (88%). Here, we describe a functional plurihormonal oncocytic adrenal cortical adenoma in a young girl, that mimicked a malignant adrenal lesion, clinically as well as on imaging and biochemical features. This report bears the objective of being aware of the atypical biochemical as well as imaging characteristics of oncocytic adrenal tumours.

Recent Advances in Stereoselective Ring Expansion of Spirocyclopropanes: Access to the Spirocyclic Compounds.

Spirocyclopropane represents a privileged structural scaffold for accessing synthetic libraries of densely functionalized spirocarbo- and heterocyclic compounds. Due to the ubiquity of spirocyclic motifs as a potent pharmacophore in natural products and pharmaceuticals, recent years have witnessed significant advances in developing synthetic strategies that exploits carbon-carbon bond scission in spirocyclopropanes. This paper summarizes the recent developments in stereoselective ring expansion of spirocyclopropanes in diversity-oriented synthesis and highlights the synthetic as well as mechanistic rationale of those methodologies. This review also encompasses the applicability of the protocols in bioactive natural product syntheses.

Stereospecific Ring Opening and Cycloisomerization of Aziridines with Propargylamines: Synthesis of Functionalized Piperazines and Tetrahydropyrazines.

Stereospecific Cu-catalyzed nucleophilic ring opening of N-sulfonylaziridines with propargylamines and subsequent hydroamination afford piperazines, which leads to double-bond isomerization to furnish tetrahydropyrazines. Optically active aziridines can be cross-coupled with high enantiomeric purities (>98% ee).