Technical Notes:

1. Biaryl bisphosphine ligand with narrow dihedral angle. The DTBM SEGPHOS? ligand, as the

ruthenium complex, gives superior enantioselectivity and diaste reoselectivity 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.4

5.With copper, enantioselective vinylsilane alkenylation of aldehydes .5

6.Gold carbene mediated stereoselective 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 carbonyl hydroacylation. 10

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

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

azabenzonorbornadienes.

13.Involved in asymmetric hydroamination of bicyclic alkenes/die nes, 13a diamination of conjugated dienes,sb and hydroalkoxylation/hydrosulfenylation of allenes.se

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

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.

19.Iridium-catalyzed intermolecular hydroamidation of olefins .

20.Iridium-catalyzed intermolecular hydroamidation of olefins.

21.CuH-catalyzed asymmetric hydroamination of olefins.