Опубликована: Ноя. 8, 2023

Spontaneous chemical reactions proceed energetically downhill to either a local or global minimum, limiting possible transformations those that are exergonic. Endergonic do not spontaneously and require an input of energy. Light has been used drive number deracemisations thermodynamically unfavourable bond-forming reactions, but is restricted substrates can absorb, directly indirectly, energy provided by photons. In contrast, anabolism involves uphill powered fuels. Here we report on the transduction from artificial fuel Diels–Alder reaction. Carboxylic acid catalysed carbodiimide-to-urea formation chemically orthogonal reaction diene dienophile, transiently brings functional groups into close proximity, causing otherwise prohibited cycloaddition in modest (12%) yield with high levels regio- (>99%) stereoselectivity (92:8 exo:endo). At fuelled steady state, kinetic asymmetry fuelling cycle ratchets away equilibrium distribution Diels–Alder:retro-Diels–Alder products. The driving endergonic occurs through ratchet mechanism, reminiscent how molecular machines directionally bias motion. Ratcheting synthesis potential expand synthetic chemistry toolbox, offering new paradigms reactivity, complexity control.

Язык: Английский