New ferrocenyloxazolines with two stereogenic centers were prepared with excellent yields starting from the (1S,2S)-(+)-2-amino-3-phenyl-1,3-propanediol. They can then be used for the preparation of ferrocenes with planar chirality with very high diastereoselectivities (>99:1%) by a lithiation/electrophile-trapping sequence. The syntheses of chiral (phosphinoferrocenyl)oxazoline and (phenylthioferrocenyl)oxazoline and their use as ligands in conjunction with bis[(π-allyl)palladium chloride] in the enantioselective allylic alkylation of rac-1,3-diphenylprop-2-enyl acetate was investigated.

Owing to the C 2 symmetry structure of 1,1‘-diphenyl-3,3‘,4,4‘-tetramethyl-2,2‘-biphosphole, 1 (BIPHOS), we investigated the coordination of this chiral bidentate ligand to transition metals in order to explore the potential of these complexes in asymmetric catalysis. Nickel, palladium, and platinum complexes [M(BIPHOS)X2] (2 (M = Ni, X = Br), 3 (M = Pd, X = Cl), 4 (M = Pt, X = Cl) were synthesized and fully characterized. Their structures were determined by X-ray crystallography. The cationic palladium complexes [Pd(BIPHOS)(CH3CN)2](BF4)2, 6, and [Pd(BIPHOS)(η3-C3H5)]Cl, 7, were also synthesized. The π-allyl−palladium complex 7 reveals a potential interest for catalytic allylic substitution. The reaction of 1 with [Pd(CH3CN)4](BF4)2 leads to the formation of the meso diastereoisomer [Pd(BIPHOS)2] (BF4)2, 5, which was fully characterized. Its structure was determined by X-ray crystallography. A bis(BIPHOS) complex of Rh(I), 8, was also obtained by reaction of 1 with [Rh(COD)Cl]2 or [Rh(COD)2]BF4.

The reaction of (5-alkynylcyclopentadienol)Co 2 (CO) 6 clusters with iron pentacarbonyl in acetone does not yield the expected product in which the hydroxyl substituent is lost and a tricarbonylcobalt vertex is replaced by an Fe(CO) 3 group. Instead, the product contains an (η 5 -C 5 Ph 2 R 2 )Fe(CO) 2 H moiety that is bridged to one of the cobalt vertexes of the intact dicobalt-alkyne cluster. The process is rationalized in terms of a decarboxylation rather than a dehydroxylation process, and the relevance to the mechanism of substitution of one metal vertex by another is discussed.