Enantiopure alkaloid mimics are synthesized via high yielding intramolecular cycloadditions of photogenerated azaxylylenes tethered to pyrroles, with further growth of molecular complexity via post-photochemical transformations of primary photoproducts. This expeditious access to structurally unprecedented polyheterocyclic cores is being developed in the context of diversity-oriented synthesis,...

The incorporation of a gem-dimethyl group at the 5-position of a chiral oxazolidinone biases the conformation of the adjacent C(4)-stereodirecting group such that the gem-dimethyl-4-iso-propyl combination mimics a C(4)-tert-butyl group, providing higher levels of stereocontrol than a simple 4-iso-propyloxazolidinone. The generality of this principle is demonstrated with applications in stereose...

Step-economical syntheses of annulated 1,2,3-triazoles were accomplished through copper-catalyzed intramolecular direct arylations in sustainable one-pot reactions. Thus, catalyzed cascade reactions involving [3 + 2]-azide-alkyne cycloadditions (CuAAC) and C-H bond functionalizations provided direct access to fully substituted 1,2,3-triazoles with excellent chemo- and regioselectivities. Likewi...

In this work we show that the regioselectivity of the Diels-Alder, 1,3-dipolar, and carbene cycloadditions to C(60) changes from the usual [6,6] addition in neutral species to the [5,6] attack when the number of electrons added to the fullerenic cage increases. Changes in the aromaticity of the five- and six-membered rings of C(60) during the reduction process provide a rationale to understand ...

Pyrrolidines are intriguing scaffolds that can be found in a variety of natural products. They have numerous biological and organocatalytic uses. The asymmetric [3+2] cycloadditions employing metal catalysis with suitable chiral ligands is robust method for the synthesis enantioenriched pyrrolidines up to four centres. Recent advances summarized Review by Guiry Kumar (DOI. 10.1002/chem.20230029...

The biologically relevant arenes ethyl salicylate and salicylic amide as well the fluorescent coumarin pyrene units were functionalized with a cyclopentadiene unit. Re 99mTc complexes of latter two synthesized fully characterized. During crystallization ligands, [2+2] [6+6] cycloadditions observed for modified coumarin. A light-induced mechanism, supported by DFT calculations, is proposed these...

Asymmetric [3+2] cycloadditions of azomethine imines comprise a useful synthetic tool for the construction of pyrazole derivatives with a variable degree of saturation and up to three stereogenic centers. As analogues of pyrrolidines and imidazolidines that are abundant among natural products, pyrazoline and pyrazolidine derivatives represent attractive synthetic targets due to their extensive ...