Toste and co-workers present a unique strategy for suppressing a unimolecular decomposition pathway of a transition-metal catalyst via architectural stabilization. The structural rigidity of metal-organic frameworks was utilized to constrain the geometry of a gold(III) catalyst to suppress catalyst decomposition by reductive elimination and, therefore, improve catalyst stability. Architectural stabilization is anticipated to serve as a general strategy for the preservation of ligand geometry in otherwise unstable systems.
A chiral mesoporous hybrid material, containing inserted bis-silylated pyrrolidine building fragments in the framework, for enantioselective Michael addition with high stereocontrol.
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