1,1-Divinyl-2-phenylcyclopropanes are entry points to a rich area of rearrangement chemistry. With N,N-diallyl amide substrates, tandem radical cyclizations can be initiated at room temperature. Warming provides products of pure thermal rearrangements with acids, ester, and amides. These isomerizations give vinylcyclopentenes resulting from divinylcyclopropane rearrangements and more deeply rea...

A new synthesis of 1-azabicyclic molecules having angular substitution is reported. This method can be employed to prepare a range of 1-azabicylic rings, including ones containing vicinal quaternary carbon centers and three contiguous stereocenters. [structure: see text]

A domino sequence has been developed between vinyldiazoacetates and racemic allyl alcohols, involving five distinct steps. The sequence generates highly functionalized cyclopentanes with four new stereogenic centers as single diastereomers in 64-92% ee. The first step is a rhodium-catalyzed oxygen ylide formation, which is then followed by a [2,3]-sigmatropic rearrangement, an oxy-Cope rearrang...

Formaldehyde (FA) is a major reactive carbonyl species (RCS) that is naturally produced in living systems through a diverse array of cellular pathways that span from epigenetic regulation to the metabolic processing of endogenous metabolites. At the same time, however, aberrant elevations in FA levels contribute to pathologies ranging from cancer and diabetes to heart, liver, and neurodegenerat...

The potential energy surface of the rearrangement of 3-vinylmethylenecyclobutane to 4-methylenecyclohexene has been studied computationally using density functional theory (B3LYP) and complete active space ab initio methods (CASSCF and CASPT2). The parent reaction is nonconcerted and occurs through several parallel diradical pathways. Transition structures and diradical intermediates are highly...

Indandione 1 was brominated to yield 2-bromoIndandione 2 which on further reacted with substituted thiocarbamides, carbamides, 2-aminothiophenols, 2-aminophenol and triazoles to furnished 3-substituted aniline-2-thia-4-aza-6,7-benzo-8-oxo-bicyclo [3.3.0]-1(5),3-octadiene 3, 3-substituted aniline-2-oxa-4-aza-6,7-benzo-8-oxo-bicyclo [3.3.0]-1(5),3-octadiene 4, 2-Thia-5-aza-9-oxo-3,4-(3’-substitut...

A four-step stereocontrolled synthesis of polyfunctionalized cis-decalins is described, involving oxidation of 2-methoxyphenol, intermolecular Diels-Alder reaction, olefination, and Cope rearrangement. Application of this efficient strategy to the total syntheses of (()-eremopetasidione, (()-3â-angeloyloxyfuranoeremophilane, and (()-3â-methacryloyloxyfuranoeremophilane was accomplished from cre...