Synthesis of N-Substituted Steroidal Hydrazides in Homogeneous Catalytic Hydrazinocarbonylation Reaction

N‐Acylhydrazines: Future Perspectives Offered by New Syntheses and Chemistry

“…[19] The same authors subsequently extended the scope of this interesting method, and demonstrated that palladium-catalysed hydrazinocarbonylation is a powerful tool for obtaining biologically important hydrazides [20] (Scheme 4). Scheme 4 A new ''one-pot'' synthesis of di-and trisubstituted hydrazides by reduction of the corresponding hydrazones and in situ acylation of the obtained hydrazine has recently been published.…”

Synthesis of new steroid-β-lactam hybrids via palladium-catalyzed aminocarbonylation

“…In the past few years, palladium-catalyzed aminocarbonylation of aryl or alkenyl halides has been investigated in our group using a great variety of nucleophilic reagents, such as primary and secondary amines [18] ammonium carbamate [19], hydrazines [20], amino acids [21e23] and ferrocenyl chalcones [24]. Mild reaction conditions and high selectivity rendered this reaction a very useful tool for the functionalization of steroidal 17-iodo-16-enes ( Fig.…”

“…Mild reaction conditions and high selectivity rendered this reaction a very useful tool for the functionalization of steroidal 17-iodo-16-enes ( Fig. 1) bearing different moieties in rings A and B [19,20,23,24]. The products were obtained in excellent yields so we decided to use this methodology to synthesize the new steroid-b-lactam hybrids.…”

“…Reaction conditions for palladium-catalyzed carbonylation were chosen according to our previous observations concerning similar reactions of steroidal substrates [19,20,23,24]. Carbonylations were carried out in the presence of the Pd(OAc) 2 e triphenylphosphane system, the catalytically active Pd(0) complex was formed in situ from the palladium salt and the phosphane [31].…”

Transition-Metal-Catalyzed Reactions in Steroid Synthesis

“…129 17-Carboxamido-androstanes possessing crown ether moieties attached to the amide functionality were synthesized from the corresponding 17-iodo-androst-16-enes. 130 Various steroidal hydrazides [131][132][133] and hydroxamic acid derivatives 134,135 were obtained by aminocarbonylation reactions using mono-or disubstituted hydrazines and either N-or O-substituted hydroxylamines as nucleophiles. As mentioned before, these reactions can be regarded as the acylation of the nucleophiles by the acylpalladium complex formed by consecutive oxidative addition-CO insertion reactions.…”