Application of (Ru((R)-BINAP)(MeCN)(1-3:5,6-eta-C8H11))(BF4) as a catalyst precursor for enantioselective hydrogenations

Article Abstract:

A catalyst system that uses (Ru((R)-BINAP(MeCN(1-3:5,5-eta,C8H11))(BF4) as a catalyst precursor has been studied. The enantioselective hydrogenations of alpha acetamidocinnamic acid, tiglic acid, itaconic acid, dimethyl itaconate, methyl tiglate, geraniol, dimethyl oxaloacetate and ethyl acetoacetate were used as a series of typical substrates. Enantioselectivities for the hydrogenation of ketones was poor to moderate, 15%-74%. It is possible that 1,4-dicarboxylate substrates with the prochiral olefin or ketone at the 2 position were hydrogenated through intermediates with similar structures.

Canada, Enantiomers, Hydrogenation, Ruthenium

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Noble gas catalysed 1,2-migrations in N2H+ and N2CH3+

Article Abstract:

Molecular orbital calculations for NH2+ and N2CH3+ and for transition structures for rearrangement of these ions by 1-2 shifts of H and CH3 have been carried out. Reaction profiles have been calculated with one noble gas atom, neon, argon, or kyrpton, present. Structure optimizations were carried out at B3LYP/6-311++G(d,p). For N2H+...M, single point calculations were also performed at QCISD(T)(full)/6-311++G(2df,p), with M one of Ne, Ar or Kr.

Molecular electronics, Krypton, Argon, Molecular orbitals

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