Addition of 2-aminobenzothiazole and substituted derivatives to mercuric acetate in warm ethanol leads to the high yield formation of [Hg{SC6H3XN(C[triple bond, length as m-dash]N)}]n resulting from loss of hydrogen and sulfur-carbon bond cleavage. Addition of phosphines affords a series of complexes in which the new ortho-cyano-aminothiophenolate ligands adopt three different binding modes.

The adduct [MeO → Bpin-Bpin](-) efficiently mediates the β-boration of α,β-unsaturated imines formed in situ. The use of chiral phosphines as additives, and in particular the chiral phosphine (S)-MeBoPhoz, enables the catalytic asymmetric reaction to proceed with higher enantioselectivity than the analogue copper(I) mediated reaction.

Chiral CuF-catalyzed asymmetric allylation of ketones and ketimines is described. Nucleophile activation via transmetallation (allylboronate to allylcopper), which is facilitated by a cocatalyst [La(OPr)3 or LiO iPr], is key for these reactions. A CuOTf–3KOtBu–DUPHOS complex is a comparably effective catalyst that reduces the required amount of chiral phosphines.

Phosphines are fundamentally important to the fine chemicals, pharmaceutical and agrochemical industries. Reported is the first example of alkene hydrophosphination using a designed iron pre-catalyst which yields the anti-Markovnikov products in high yield at room temperature. The phosphine products are excellent pro-ligands for Fe-catalyzed Negishi cross-coupling.

A general, atom-economical method for the synthesis of phosphaalkenes is reported via the net coupling of primary alkyl or aryl phosphines with aryl or alkyl isocyanides at zirconium. The phosphorus-containing ligand can be liberated as the phosphaformamide from zirconium by reaction with an organic electrophile.

[reaction: see text] An ortho-substituted BIPHEP ligand, o-Ph-hexaMeO-BIPHEP (1), is designed and synthesized. Compared with chiral biaryl phosphines without ortho substituents such as BINAP and MeO-BIPHEP, o-Ph-hexaMeO-BIPHEP shows higher enantioselectivities in Rh-catalyzed hydrogenation of cyclic enamides.

A new series of chiral ferrocenyl bis-phosphine ligands have been synthesized. Elements of planar and central chirality have been incorporated into a ferrocene backbone through sulfinyl, sulfonyl and sulfenyl groups at the ortho-position to the phosphines. The effectiveness of these ligands has been demonstrated in Rh-catalyzed hydrogenations and Pd-catalyzed allylic alkylations. 2005 Elsevier ...