[reaction: see text] The synthesis of primary amines via reductive amination of the corresponding carbonyl compounds with aqueous ammonia is achieved for the first time with soluble transition metal complexes. Up to an 86% yield and a 97% selectivity for benzylamines were obtained in the case of various benzaldehydes by using a Rh-catalyst together with water-soluble phosphine and ammonium acetate. In the case of aliphatic aldehydes, a bimetallic catalyst based on Rh/Ir gave improved results.

[reaction: see text] Organocatalytic asymmetric Mannich reaction of protected amino ketones with imines in the presence of an L-proline-derived tetrazole catalyst afforded diamines with excellent yields and enantioselectivities of up to 99%. The amino ketone protecting group controlled the regioselectivity of the reaction providing access to chiral 1,2-diamines from azido ketones and 1,4-diamines from phthalimido ketones.

The carbonylative opening of terminal epoxides under mild conditions has been developed using Co2(CO)8 as the catalyst. Under 1 atm of carbon monoxide and at room temperature in methanol, propylene oxide is converted to methyl 3-hydroxybutanoate in up to 89% yield. This transformation is general for many terminal epoxides bearing alkyl, alkenyl, aryl, alkoxy, chloromethyl, phthalimido, and acetal functional groups. The opening takes place without epimerization at the secondary stereocenter.

Supporting InformationGeneral. Chemicals and solvents were either purchased puriss p.A. from commercial suppliers or purified by standard techniques. For thin-layer chromatography (TLC), silica gel plates Merck 60 F254 were used and compounds were visualized by irradiation with UV light and/or by treatment with a solution of p-anisaldehyde (23 mL), conc. H 2 SO 4 (35 mL), acetic acid (10 mL), and ethanol (900 mL) followed by heating. Flash chromatography was performed using silica gel Merck 60 (particle size 0.040-0.063 mm), 1 H NMR and 13 C NMR spectra were recorded on Bruker DRX-400, DRX-500 MHz. Chemical shifts are given in δ relative to tetramethylsilane (TMS), the coupling constants J are given in Hz. The spectra were recorded in CDCl 3 as solvent at room temperature, TMS served as internal standard (δ = 0 ppm) for 1 H NMR, and CDCl 3 was used as internal standard (δ = 77.0 ppm) for 13 C NMR. HPLC was carried out using a Hitachi organizer consisting of a D-2500 Chromato-Integrator, a L-4000 UV-Detector, and a L-6200A Intelligent Pump. Optical rotations were recorded on a Perkin Elemer 241 Polarimeter (λ=589 nm, 1 dm cell). High-resolution mass spectra were recorded on an IonSpec FTMS mass spectrometer with a DHB-matrix. 1): To a glass vial charged with imine (0.5 mmol) in solvent (1 mL) was added ketone (0.75 mmol) followed by catalyst (30 mol%) and the reaction was stirred until completion as monitored by TLC. Then, a half saturated NH 4 Cl solution and ethyl acetate were added with vigorous stirring, General experimental procedure for two-component Mannich reaction (Table

Pressure. -The mild and practical transformation proceeds without epimerization. The internal epoxide (V) reacts analogously. -(DENMARK*, S. E.; AHMAD, M.; J. Org. Chem. 72 (2007) 25, 9630-9634; Dep. Chem., Univ. Ill., Urbana, IL 61801, USA; Eng.) -Jannicke 17-102