The Longuet-Higgins phase change theorem is used to show that, in certain photochemical reactions, a single product is formed via a conical intersection. The cis-trans isomerization around the double bond in the formaldiminium cation and vinylamine are shown to be possible examples. This situation is expected to hold when the reactant can be converted to the product via two distinct elementary ...

We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopen...

1,4-Benzoquinones have been found to prevent olefin isomerization of a number of allylic ethers and long-chain aliphatic alkenes during ruthenium-catalyzed olefin metathesis reactions. Electron-deficient benzoquinones are the most effective additives for the prevention of olefin migration. This mild, inexpensive, and effective method to block olefin isomerization increases the synthetic utility...

Sub-picosecond photo-isomerization is the major primary process of energy conversion in retinal proteins and has as such been focus extensive theoretical experimental work over past decades. In this review article, we revisit long-standing question to how protein tunes isomerization speed quantum yield. We on our recent contributions field, which underscore concept a delicate mixing reactive no...