Technical Notes:

1. Biaryl bisphosphine ligand with narrow dihedral angle. The DTBM SEGPHOS? ligand, as the ruthenium complex, gives superior enantioselectivity and diastereoselectivity through dynamic kinetic resolution in the asymmetric hydrogenation of a-substituted-?-ketoesters useful in the synthesis of carbapenum antibiotics.

2.With rhodium, preferential enantioselective hydrogenation of more reactive olefin of extended enone structure.

3.Rhodium catalyzed chemo-, regio, and entantioselective2 + 2 + 2cycloaddition of alkynes with isocyanates .

4.With copper, enantioselective cross Aldol-type reaction of acetonitrile.

5.With copper, enantioselective vinylsilane alkenylation of aldehydes.

6.Gold carbene mediated ste reoselective cyclopropanation of propargyl esters.

7.With copper, enantioselective 1 ,2-reduction of ketones, and 1 ,4-reduction of a a, ?-usaturatedesters

8.With copper, catalytic enantioselective Mannich-type reaction.

9.Enantioselective fluorination of b ?-keto esters, tert butoxycarbonyl lactones and lactmes with Sodeoka's Pd-aqua complex and a fluorinating reagent.

10.Rh-catalyzed intramolecular olefin or carbonyI hydroacylation.

11.Pd-catalyzed y-arylation of ?,y-unsaturated ketones .

12.Involved in numerous conjugate alkynylation, and ring-opening alkynylation of azabenzonorbornadienes.

13.Involved in asymmetric hydroamination of bicyclic alkenes/dienes,13a diamination of conjugated dienes, 13b and hydroalkoxylation/hydrosulfenylation of allenes.

14.Used in cycloaddition reactions such as 1,3- dipolar cycloaddition of azomethine ylides, and Au-catalyzed2+2cycoaddition of allenes.14b

15.Asymmetric conjugate addition of nitroalkanes to a,?-usaturated thioamides .

16.Asymmetric synthesis of isothiazoles through Cu catalyzed conjugate addition of allyl cyanide to a,?-usaturated thioamides.

17.Asymmetric Ag-catalyzed cycloadditions.

18.Rhodium-catalyzed c C bond cleavage to generate acyclic, asymmetric quaternary centers .

19Iridium-catalyzed intermolecular hydroamidation of olefins.

20.Palladium-Catalyzed Asymmetric Hydrogenation of a-Acyloxy-1 -arylethanones.