Technical Notes :

1. Biaryl bisphos phine ligand with narrow dihedral angle. The SEGPHOS? ligand has been applied

to a variety of metal catalyzed re actions. In many cases, yields and enantios electivities, exceed results obtained earlier using BINAP.1',2

2.As ruthenium complex, SEGPHOS? generally gives higher levels of chiral induction in as ymmetric hydrogenations of a,? , and y-functionalized ketones. See ruthenium complexes 44-0096, 44-0518,44-0168.

3.Used in Rh-catalyzed transformations such as: (a) 1 ,4-addition of boronic acids to coumarins, (b) addition of titanium reagents to imines,' (c) cotrimerization of alkenes and acetylenes,"o (d)

double2+2+2cycloaddition,'' (e) indanone formation.

4. Used in Pd-catalyzed transformations such as: (a) cycloaddition of 1,6-enyne,' (b) arylative cyclization of allenyl aldehydes with boronic acids, s (c) synthesis of chromans .

5. Used in Cu-catalyzed transformations such as: (a) nitroso Diels-Alder,' (b) reductive aldol

condensation, (c) conjugate reduction of uns aturated sulfones,'5 and phophonates Iridium-catalyzed asymmetric hydrogenation of quinolines activated by chloroformates,

Iridium-catalyzed asymmetric transfer hydrog enation used in polyketide construction.

8.Rhodium-catalyzed as ymmetric hydroarylation of 3-pyrrolines.'

9. P alladium-catalyzed regio- and enantios elective dearomatization of pyrroles to 2H-pyrroles.19 10. 10.Rhodium- catalyzed as ymmetric s ynthesis of cyclopentanols 20

11Silver-catalyzed asymmetric Mannich-type reaction.