New Synthetic Route to Pheniramines via Hydroformylation of Functionalyzed Olefins

Hydroaminomethylation with Novel Rhodium–Carbene complexes: An Efficient Catalytic Approach to Pharmaceuticals

“…Figure 2 the central rhodium atom is coordinated by the 1,3-cyclooctadiene unit, the chlorine atom and the corresponding carbene ligand in a contorted square planar coordination in 1, 2 and 4. The distance between the rhodium and the carbene atom varies between 2.049 (16) and 2.067 (5) , which is equal within the measurements failure. Surprisingly, the substituents on the carbene backbone, the methyl groups in complex 2 or the chloro substitution in complex 4 do not influence significantly the carbene-rhodium bond length or carbon À carbon double bond length within the imidazole ring.…”

“…In this regard the work of Botteghi et al is noteworthy, who for the first time described the synthesis of 3,3-diphenylpropylamines using a sequential hydroformylation-reductive amination sequence (Scheme 2). [5] The overall yields of the synthesis range between 60 and 70 %. Comparably good results have been obtained in the preparation of pheniramines starting from acetals.…”

Highly Regioselective Rhodium‐Catalysed Hydroformylation of Unsaturated Esters: The First Practical Method for Quaternary Selective Carbonylation

“…In particular, there are a couple of isolated examples of chelation controlled quaternary selective hydroformylation reactions. [20][21][22][23] In these examples, the preferential formation of a quaternary rhodium alkyl species stabilised by a second chelate interaction seems the most likely explanation for the selectivity observed. More relevantly, Alper and co-workers had shown that hydroformylation of methyl methacrylate using [RhA C H T U N G T R E N N U N G (cod)(h 6 -C 6 H 5 -BPh 3 )] and dppb (cod = cyclooctadiene, dppb = 1,2-bis(diphenylphosphano)benzene) as ligand gave a 54 % yield of the quaternary aldehyde, Me 2 CA C H T U N G T R E N N U N G (CHO)A C H T U N G T R E N N U N G (CO 2 Me) with 9:1 regioselectivity.…”

Zwitterionische Verwandte kationischer Platinmetallkomplexe: Anwendungen in der stöchiometrischen und katalytischen σ‐Bindungsaktivierung

“…In nachfolgenden Arbeiten von Alper et al 38–61. sowie von anderen Gruppen62–69 wurden 3 und ähnliche Phenylborat‐Zwitterionen in verschiedenen Umwandlungen unter Spaltung und/oder Bildung von E‐H‐ und E‐C‐σ‐Bindungen verwendet (Schema ), einschließlich der Hydroformylierung von Alkenen und Alkinen,37, 39, 42–44, 48, 54–56, 62, 63, 69 der Germyl‐ und Silylformylierung (Silylhydroformylierung) von Alkinen,46, 49, 50, 53, 67, 68 der reduktiven Carbonylierung von Alkenen,38 der Carbonylierung und/oder Cyclisierung von Allylaminen und ‐bromiden,41, 47 Hydrocarbonylierungen und Silylcarbonylierungen,57, 60, 61, 64 der Hydroaminomethylierung und Hydroaminovinylierung von Alkenen,58, 59, 65, 66 Hydrosilylierung von Ketonen40 und Hydrierung von Iminen 51. Außerdem fanden 3 und verwandte Zwitterionen Anwendung als Präkatalysatoren in der Alkinpolymerisation (Schema ) 45.…”