Proline-catalysed asymmetric direct aldol reaction of different aromatic aldehydes with acetone and several other ketones in the room temperature ionic liquid 1-n-butyl-3-methylimidazolium hexafluorophosphate achieved good yields of aldolisation products with reasonable enantioselectivities, even when just 1-5% of proline was used as the catalyst; immobilisation of the catalyst in an ionic liquid phase offers simple product isolation and reuse of the catalytical system in subsequent reactions.

Aminoferrocene has been converted into formamidoferrocene, which exists in solution as an equilibrium mixture of two rotational isomers, a monomeric cis form and a dimeric (or oligomeric) trans form. Variable-temperature and 13(3{ | NMR spectra have been used to measure AG* for the hindered internal rotation about the C-N bond. Dehydration of formamidoferrocene yields isocyanoferrocene, which has been characterized by complex formation with iron and molybdenum carbonyls. A high-yield conversion of aminoferrocene into isothiocyanatoferrocene is described. co-workers. This paper describes the preparation of two other simple nitrogen-substituted ferrocenes, namely isocyanoferrocene, FcNC,38 and isothiocyanatoferrocene, FcNCS, and some related chemistry. Results and DiscussionAlkyl and aryl isocyanides have been extensively employed as ligands in organometallic chemistry since they are analogous to, but more basic than, carbon monoxide.11 Aryl isocyanides are better -acceptors than alkyl isocyanides.12 A wide range of substituted aryl isocyanides is now readily accessible, due to the development by Ugi and co-workers13 of substituent-tolerant formamide dehydration procedures that are more versatile than the historically interesting carbylamine reaction.14 Surprisingly, isocyanoferrocene has not been described, although it might be expected to be a stronger -donor but a slightly weaker -acceptor14 than isocyanobenzene. Each of the f Dedicated to Professor Lord Tedder on the occasion of his retirement.

Enantioselective allylic substitution reactions of (rac)-(E)-1,3-diphenyl-3-acetoxyprop-1-ene with dimethyl malonate (DMM) are studied in 1-butyl-3-methylimidazolinium hexafluorophosphate ([bmim][PF 6 ]) as an ionic solvent; the reactions are catalyzed by Pd 0 complexes of two homochiral ferrocenylphosphine ligands, (S,R)-BPPFA and (R,S)-BPPFDEA with the recycling of the catalytic system being tested. A similar reaction with 1-phenyl-3-acetoxyprop-1-ene is also studied with only a linear achiral product being isolated.

Enantioselective Pd-catalyzed allylic substitution of (rac)-(E)-1,3-diphenyl-3-acetoxyprop-1-ene with dimethyl malonate was studied in 3-butyl-1-methylimidazolium hexafluorophosphate ([bmim][PF 6 ]) as an ionic liquid. The reactions were catalyzed by Pd(0) complexes of three homochiral ferrocenylphosphine ligands, (S,S)-iPr-Phosferrox, (S,R)-iPr-Phosferrox, (R,S)-BCyPFA and (R)-BINAP. Potassium carbonate and bis(trimethylsilyl)acetamide (BSA)/AcOK were tested as the bases and simple optimization of the reaction procedure was performed. Experiments with other soft nucleophiles also were carried out under optimized conditions.