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Conceptually new bifunctional chiral ligands were developed. The axially chiral N,N-bidentate phenanthroline ligand (S)-1 was found to be effective for Pd-catalyzed asymmetric allylic substitution of allyl acetate and dialkyl malonate. The intramolecular Lewis basic group from the hydroxybinaphthyl structure of (S)-1 played a pivotal role in the high reactivity and enantioselectivity. [ABSTRACT FROM AUTHOR]

Several transition-metal complexes that bind the bis(oxazolinyl)phenyl moiety as a tridentate ligand have been prepared to showcase their highly potent activities for asymmetric catalysis in conjugate reductions, reductive aldol reactions, direct aldol reactions and hydrogenation reactions. Some reactions of the metals were also examined. [ABSTRACT FROM AUTHOR]

The first transfer-hydrogenative cyclization of 1,6-diynes that leads to exocyclic dienes was developed using a ruthenium catalyst and MeOH as a H2surrogate. [ABSTRACT FROM AUTHOR]

A ruthenium cyclic biscarbene complex reacted with a H2O molecule under mild conditions to produce η5-oxapentadienyl complex, that proved to be the intermediate in the catalytic hydrative cyclization of a diyne. [ABSTRACT FROM AUTHOR]

A chirality switch between novel NCN pincer Rh complexes and a related double cyclometalated NCNC Rh complex containing secondary amino groups is described. Their catalytic abilities were determined in asymmetric alkynylation of ethyl trifluoropyruvate, and the change in the coordination geometry of the Rh catalysts affected the stereochemistry of the products.

The novel N,N,O-tridentate phenanthroline ligand (BinThro) bearing an axially chiral binaphthyl backbone prepared from BINOL was found to be an effective chiral catalyst for enantioselective addition of diethylzinc to aromatic aldehydes with high enantioselectivity (up to 95% ee).

The first catalytic synthesis of exocyclic 1,3-dienylphosphine oxides was achieved by the ruthenium-catalyzed selective hydrophosphinylative cyclization of 1,6-diynes. A plausible mechanism involving a ruthenacyclopentatriene intermediate is proposed on the basis of the DFT calculations of model ruthenium complexes.

Bis(oxazolinyl)phenyl ruthenium(II) complexes were found to catalyze asymmetric hydrogenation of ketones, in which chiral bulky alcohol additives showed significant enhancement of enantioselectivity even in protic solvents.

The first transfer-hydrogenative cyclization of 1,6-diynes that leads to exocyclic dienes was developed using a ruthenium catalyst and MeOH as a H(2) surrogate., (This journal is © The Royal Society of Chemistry 2011)

Chiral rhodium-bisoxazolinylphenyl acetate complexes exhibited high catalytic activity for the beta-boration of alpha,beta-unsaturated carbonyl compounds with bis(pinacolato)diboron in the presence of sodium t-butoxide with enantioselectivity up to 97%.

New bis(oxazolinyl)phenyl-ruthenium(II) complexes, which were synthesized by C-H bond activation with RuCl(3).3H(2)O in zinc powder and 1,5-cyclooctadine followed by ligand exchange reaction with sodium acetylacetonate or acetylacetone, exhibited enantioselective hydrogenation of ketones in up to 90% ee.

The combination of Fe(OAc)2 and multi-nitrogen-based ligands such as N,N,N',N'-tetramethyethylenediamine, bis-tert-butyl-bipyridine, or bis(oxazolinyl)pyridine can efficiently catalyse hydrosilylation of ketones to give the corresponding alcohols in high yields including asymmetric catalysis.

In the presence of 5-10 mol% Cp*RuCl(cod), 1,6- and 1,7-diynes were allowed to react with an ethynylboronate at ambient temperature to give rise to bi- and tricyclic arylboronates in 64-93% isolated yields.

In the presence of catalytic amounts of Cp*RuCl(cod), the partially intramolecular cyclotrimerizations of various C-alkynylglycosides and C-diynylglycosides proceeded at ambient temperature to afford C-arylglycosides.

In the presence of catalytic amounts of Cp*RuCl(cod), the cycloaddition of 1,6-diynes with various C-alkynylglycosides proceeded at ambient temperature to afford C-arylglycosides in 46-93% yields.

In the presence of a catalytic amount of Cp*RuCl(cod), 1,6- and 1,7-diynes connected by an amide or an ester tether underwent cycloaddition with terminal alkynes at room temperature to give rise to cycloadducts in 40-93% yields with 63 : 37-83 : 17 regioisomer ratios.