Search

Derivatives of the fully twisted bicyclic amide 7-hypoquinuclidone are synthesized using a Schmidt--Aubé reaction. Their structures were unambiguously confirmed by X-ray diffraction analysis and extensive spectroscopic characterization. Furthermore, the stability and chemical reactivity of these anti-Bredt amides are investigated. 7-Hypoquinuclidonium tetrafluoroborate is shown to decompose to a unique nitrogen bound amide--BF3 complex of 7-hypoquinuclidone under anhydrous conditions and to react instantaneously with water making it one of the most reactive amides known to date. [ABSTRACT FROM AUTHOR]

Though Lewis acids (LAs) have been shown to have profound effects on carbon dioxide (CO 2 ) reduction catalysis, the underlying cause of the improved reactivity remains unclear. Herein, we report a well-defined molecular system for probing the role of LA additives in the reduction of CO 2 to carbon monoxide (CO) and water. Mo(0) CO 2 complex (2) forms adducts with a series of LAs, demonstrating CO 2 activation that correlates linearly with the strength of the LA. Protons induce C-O cleavage of these LA adducts, in contrast to the CO 2 displacement primarily observed in the absence of LA. CO 2 cleavage shows dependence on both bond activation and the residence time of the bound small molecule, demonstrating the influence of both kinetic and thermodynamic factors on promoting productive CO 2 reduction chemistry.