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The design, atomic characterization, performance, and relevance to clean technology of two distinct categories of new nanocatalysts are described and interpreted. Exceptional molecular selectivity and high activity are exhibited by these catalysts. The first category consists of extended, crystallographically ordered inorganic solids possessing nanopores (apertures, cages, and channels), the diameters of which fall in the range of about 0.4 to about 1.5 nm, and the second of discrete bimetallic nanoparticles of diameter 1 to 2 nm, distributed more or less uniformly along the inner walls of mesoporous (ca. 3 to 10 nm diameter) silica supports. Using the principles and practices of solid-state and organometallic chemistry and advanced physico-chemical techniques for in situ and ex situ characterization, a variety of powerful new catalysts has been evolved. Apart from those that, inter alia, simulate the behavior of enzymes in their specificity, shape selectivity, regio-selectivity, and ability to function under ambient conditions, many of these new nanocatalysts are also viable as agents for effecting commercially significant processes in a clean, benign, solvent-free, single-step fashion. In particular, a bifunctional, molecular sieve nanopore catalyst is described that converts cyclohexanone in air and ammonia to its oxime and caprolactam, and a bimetallic nanoparticle catalyst that selectively converts cyclic polyenes into desirable intermediates. Nanocatalysts in the first category are especially effective in facilitating highly selective oxidations in air, and those in the second are well suited to effecting rapid and selective hydrogenations of a range of organic compounds.
Chem Rec 2001
PMID:Nanopore and nanoparticle catalysts. 1193 51

The Ferrier carbocyclization reaction is one of the most powerful transformations of carbohydrates. This reaction provides enantiomerically pure cyclohexanone derivatives from aldohexoses, and is particularly useful in the chiral pool synthesis of cyclohexane-containing natural products from carbohydrates. We have investigated the synthesis of natural products utilizing the Ferrier carbocyclization reaction. This account provides a brief overview of the Ferrier carbocyclization and its application to natural product synthesis. The utility and versatility of the Ferrier carbocyclization reaction are showcased with the syntheses of hygromycin A, lycoricidine, actinobolin, galanthamine, and morphine starting from carbohydrates.
Chem Rec 2014 Aug
PMID:Synthesis of natural products containing cyclohexane units utilizing the Ferrier carbocyclization reaction. 2504 63