Phosphine-catalyzed [3+2]cycloaddition reactions of electron-deficient allenes and alkynes with a,b-unsaturated carbonyl compounds can give access to important highly functionalized cyclopentenes. The seminal example of such a transformation was first reported by Lu et al. in 1995, and its asymmetric version in 1997 by the group of Zhang. However, it took another ten years before the potential ...

Aplydactone (1) is a brominated ladderane sesquiterpenoid that was isolated from the sea hare Aplysia dactylomela together with the chamigranes dactylone (2) and 10-epi-dactylone (3). Given the habitat of A. dactylomela, it seems likely that 1 is formed from 2 through a photochemical [2 + 2] cycloaddition. Here, we disclose a concise synthesis of 1, 2, and 3 that was guided by excited state the...

The cycloaddition reaction of diphenylketene and cycloheptatriene is studied. The reaction proceeds via a highly asynchronous reaction path to the zwitterionic 6 as intermediate. Subsequent CC- bond formation yields 8, 8 diphenylbicyclo [4. 2. I] nona-2, 4-dien-7-one (1) and 7,7-diphenylbicycol [3.2.2] nona-2, 8-dien-ri-one (2) in a 1:1 ratio as formal [6+2] and [4+2] cycloaddition products

This work presents the desymmetrization of oxabenzonorbornadienes through (3+2) cycloaddition reaction with hydrazones using a chiral Brønsted acid such as BINOL-derived phosphoramide. catalyst appears most effective mediator for activation hydrazone via hydrazonium cation that reacts in fashion oxabenzonorbornadiene olefinic counterpart. Under optimized conditions, provided selectively exo pro...