[3+2] Cascade Ring-Closing/Ring-Opening Strategy: Access to N-Indene-Tethered Amino Alcohols.

An unprecedented atom-economic redox neutral regioselective Rh(III)-catalyzed cascade [3+2] annulation of 2-aryl oxazoline with α,ß-unsaturated nitro olefins has been accomplished, furnishing a novel set of nitro-functionalized indene-tethered amino alcohols through a synergistic ring-closing/ring-opening strategy via the formation of two new C-C bonds and the regioselective cleavage of the C2-O bond of oxazoline under silver free mild reaction conditions with a broad substrate scope.

A condition-tuned unorthodox approach to indole-3-carboxylic acids and anthranilic acids via carbon atom translocation.

We describe a robust one-pot cascade method for the synthesis of indole-3-carboxylic acids using isatins and DMSO via a one-carbon translocation involving in situ generation of α,ß-unsaturated methylvinylsulfoxide followed by amide bond cleavage and ring closure. The methodology has been extended to afford anthranilic acid derivatives by tuning the reaction conditions in the presence of molecular oxygen. Importantly, easy access to commercially available drugs, including tropisetron, is demonstrated.

Electrochemical C(sp3)-C(sp3) cross-dehydrogenative coupling: enabling access to 9-substituted fluorescent acridanes.

A straightforward strategy for direct access of C9-functionalized N-alkyl-acridanes in good to excellent yields has been established via a metal- and external oxidant-free sustainable electrochemical C(sp3)-C(sp3) cross-dehydrogenative coupling reaction between acridanes and benzo fused lactones at ambient temperature. A broad substrate scope with superior functional-group tolerance via anodic oxidation of acridanes permitted the synthesis of a vast spectrum of fluorescence-active acridanes with high quantum yields.

Synthesis of indene-fused spiro-dibenz(ox)azepines via Rh(III)-catalyzed cascade regioselective C-H activation/annulation.

We report an unprecedented atom-economic one-pot Cp*Rh(III)-catalyzed regioselective [3+2]-spiroannulation reaction between dibenz(ox)azepines and ynones, allowing the synthesis of biologically relevant novel spirocyclic dibenz(ox)azepines under operationally simple and mild reaction conditions. The reaction proceeds without any silver additive or external oxidant implementing a redox-neutral pathway. A broad substrate scope with diverse functional group tolerance permitted the regioselective synthesis of a wide spectrum of indene-containing spirocyclic dibenz(ox)azepines in good to excellent yields. Also, we showcased detailed mechanistic studies to justify the formation of spirocycles. In addition, the synthetic utility of this process was also demonstrated by the modular synthesis of various steroid conjugates.

Regio- and Diastereoselective [3 + 2]-Spiroannulation of Benzoxazines with Chalcones: A Rh(III)-Catalyzed Redox-Neutral Approach to α-Aroyl Spiro-Indanamines.

We report an atom-economic Rh(III)-catalyzed [3 + 2]-spiroannulation reaction between cyclic ketimines and α,ß-unsaturated carbonyl compounds, allowing the synthesis of novel spirocycles with concomitant generation of three stereogenic centers in one pot. The reaction does not require any silver additives or external oxidants and is believed to proceed in a redox-neutral manner. A broad substrate scope with good functional group tolerance permitted the synthesis of a vast spectrum of spirocyclic 1,4-benzoxazine derivatives containing polysubstituted α-aroyl-indanamines in good to excellent yields with high diastereoselectivity.

A radical-radical cross-coupling reaction of xanthene with sulfonyl hydrazides: facile access to xanthen-9-sulfone derivatives.

A straightforward strategy for direct incorporation of sulfonyl units into a xanthene moiety for accessing xanthen-9-sulfone derivatives in good to excellent yields has been established via metal-free radical-radical cross-coupling reaction of xanthenes and sulfonyl hydrazides. Using easily accessible starting materials, this methodology proceeds efficiently with a high degree of functional group compatibility and with a wide scope of both xanthenes and sulfonyl hydrazides under operationally simple reaction conditions. Mechanistic investigations revealed that sulfonyl radicals could be generated from sulfonyl hydrazides in the presence of TBHP under an oxygen atmosphere.