ABSTRACT
A doubly-interlocked [2]catenane - or Solomon link - undergoes a complex conformational change upon addition of sulfate in methanol. This transformation generates a single pocket where two SO42- anions bind through multiple hydrogen bonds and electrostatic interactions. Despite the close proximity of the two anions, binding is highly cooperative.
ABSTRACT
Herein, we report the synthesis of highly reduced bipyridyl magnesium complexes and the first example of a stable organic magnesium electride supported by quantum mechanical computations and X-ray diffraction. These complexes serve as unconventional homogeneous reductants due to their high solubility, modular redox potentials, and formation of insoluble, non-coordinating byproducts. The applicability of these reductants is showcased by accessing low-valent (bipy)2Ni(0) species that are challenging to access otherwise.
ABSTRACT
We report a Ti(OiPr)4-mediated multicomponent reaction, which produces 3,4-substituted cis-δ-lactones from alkyl magnesium chloride, benzaldehyde and CO2. The key intermediate, titanacyclopropane, is formed in situ from Ti(OiPr)4 and a Grignard reagent, which enables 1,2-dinucleophilic reactivity that is used to insert carbon dioxide and an aldehyde. An alternative reaction route is also described where a primary alkene is used to create the titanacyclopropane. A computational analysis of the elementary steps shows that the carbon dioxide and the aldehyde insertion proceeds through an inner-sphere mechanism. A variety of cis-butyrolactones can be synthesized with up to 7 : 1 diastereoselectivity and 77% yield.
