Cationic [Rh(cod)2]+BF4− and various phosphines were employed as in situ catalysts for the first regiospecific anti‐Markovnikov hydroamination of aromatic olefins, particularly styrene and substituted styrenes (see diagram). Hydroamination with secondary aliphatic amines, especially morpholine and N‐arylpiperazines, was also achieved in the presence of these catalysts. Kinetic studies and isotopic labeling experiments gave insight into the possible reaction pathways. The parameters which influence the amination yield and product ratios were investigated in detail.

Primary and unbranched secondary amines are obtained by the highly selective hydroaminomethylation of olefins with ammonia [Eq. (a)]. The selectivity is readily controlled with a new dual Rh/Ir catalyst in a two-phase system.

The applications of catal~ic transformations of SO 2 into sulfur-containing organic compounds, reported in the literature, are briefly reviewed. The authors" studies in this field of chemistry, viz., the hydrosulfination of alkenes, the synthesis of ~,-o• sulfones via hydrosulfination, and the synthesis of aromatic sulfinie acids from diazonium salts, are summarized. Current results on the synthesis of the new sullqnato complex [Pd(SO2Ph)(CIMppp I and its hydrogenation to PhSO2H are presented, and a mechanism for the catalytic synthesis of sulfinic acids is proposed. The structure of {[Pd(p-CI)(dppp)]2}2+(SO4) 2-. 4SO 2 salt is studied by X-ray diffraction analysis.

The solubility of the modifying ligand is an important parameter for the efficiency of a rhodiumcatalysed hydroformylation system. A facile synthetic procedure for the preparation of well-defined xanthene-type ligands was developed in order to study the influence of alkyl substituents at the 2-, and 7-positions of the 9,9-dimethylxanthene backbone and at the 2-, and 8-positions of the phenoxaphosphino moiety of ligands 1 ± 16 on solubility in toluene and the influence of these substituents on the performance of the ligands in the rhodium-catalysed hydroformylation. An increase in solubility from 2.3 mmol ¥ L À 1 to > 495 mmol ¥ L À 1 was observed from the least soluble to the most soluble ligand. A solubility of at least 58 mmol ¥ L À 1 was estimated to be sufficient for a large-scale application of these ligands in hydroformylation. Highly active and selective catalysts for the rhodium-catalysed hydroformylation of 1-octene and trans-2-octene to nonanal, and for the hydroformylation of 2-pentene to hexanal were obtained by employing these ligands. Average rates of > 1600 (mol aldehyde) Â (mol Rh)¼ 637 mM} and excellent regio-selectivities of up to 99% toward the linear product were obtained when 1-octene was used as substrate. For internal olefins average rates of > 145 (mol aldehyde) Â (mol Rh)À 1 Â h À 1 {p(CO/ H 2 ) ¼ 3.6 ± 10 bar, T ¼ 393 K, [Rh] ¼ 1 mM, [alkene] ¼ 640 ± 928 mM} and high regio-selectivities up to 91% toward the linear product were obtained.

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