Polycyclic Pyrazoles from Alkynyl Cyclohexadienones and Nonstabilized Diazoalkanes via [3 + 2]-Cycloaddition/[1,5]-Sigmatropic Rearrangement/Aza-Michael Reaction Cascade.

An efficient method for the stereoselective synthesis of "all center substituted" polycyclic pyrazoles from alkynyl cyclohexa-2,5-dienones and nonstabilized diazoalkanes via sequential [3 + 2]-cycloaddition/[1,5]-sigmatropic rearrangement and aza-Michael reactions is reported. The developed process is highly regioselective and stereoselective. It employs a wide substrate scope to furnish structurally diverse linear and bridged [4.

Direct Use of Phosphonium Salts for Alkylation of -Quinols: Formal α-Arylation of Carbonyls via a 5-Membered Betaine-Type Intermediate.

Unlike phosphonium ylides used extensively for C═C bond formation, herein we disclose the direct use of phosphonium salts for site-selective alkylation to -quinols via a 5-membered betaine-type intermediate. This strategy provides a novel and general approach for the synthesis of α-(-aminoaryl) esters, amides and ketones under ambient conditions. The reaction proceeds through in situ generation of P-ylide, alkylation and aromatization.

Catalytic Friedel-Crafts Alkylative Desymmetrization of Cyclohexa-2,5-dienones: Access to Linear and Bridged Polycyclic Pyrroles and 3-Arylpyrroles.

A catalytic [3 + 2]-cycloaddition/Friedel-Crafts alkylative desymmetrization strategy has been developed for the stereoselective construction of linear and bridged polycyclic pyrroles from alkynylcyclohexa-2,5-dienones. This strategy was further explored for the synthesis of 3-arylpyrroles under Brønsted acid catalysis. Reaction is highly chemo-, regio-, and stereoselective and is compatible with wide range of functionalized cyclohexa-2,5-dienones/pyrroles (>51 examples, ≤98% yields).