Systematic investigation on the synthesis of androstane-based 3-, 11- and 17-carboxamides via palladium-catalyzed aminocarbonylation

Palladium-catalyzed diaminocarbonylation: synthesis of androstene dimers containing 3,3′- or 17,17′-dicarboxamide spacers

“…Based on our previous studies on the aminocarbonylation of steroidal iodoalkenes [11][12][13][14][15][16], we aimed at the synthesis of steroidal dimers containing 3,3 0 -and 17,17 0 -dicarboxamide spacers. Especially dicarboxamides possessing further functionality(ies) in the A-ring are of special interest.…”

“…A wellknown robust palladium(0) catalyst, formed 'in situ' from palladium(II) acetate and two molar equivalents of triphenylphosphine, has been used in all carbonylation experiments [34]. It has to be added that in general, acceptable yields can be achieved in aminocarbonylation of similar steroidal iodoalkenes (possessing 17-iodo-16-ene and 3-iodo-3,5-diene functionalities) with primary and secondary amines as N-nucleophiles under mild conditions (1 bar CO, 50-60°C) [1, [13][14][15]. The observations are in agreement with those results obtained with model substrates possessing the iodoalkene functionality [35].…”

“…Aminocarbonylation has been favorably used for the introduction of a carboxamide functionality either at the sterically more hindered 12-and 11-positions of the C-ring [11,12] or for the selective functionalization at 3-, 11-, and 17-positions using androstanes possessing 3-iodo-4-ene, 11-iodo-9(11)-ene, and/or 17-iodo-16-ene moieties [13,14]. A similar methodology has been used for the synthesis of analogous compounds in the 13a-series [15] and functionalized D-homo-androstanes and -estranes [16].…”

Modellvegyületektől a gyakorlati fontosságú származékokig: barangolásaim a szervetlen és szerves kémia határterületein

“…Ábra). A 11-karbonsavamidok kiépítését a 3-keto és a 17-keto csoportok védése után is megvalósítottuk a 11-keto-csoportból kialakított 11-jód-11-én aminokarbonilezésével 36 (39. Ábra).…”

Transition‐Metal‐Mediated or ‐Catalyzed Syntheses of Steroids and Steroid‐Like Compounds

“…[31] In a similar manner, Pd-based methodology was used for attachment of the carboxyamido group on the A, [32] C, [32,33] and D [32,34] rings of various steroids or their congeners by Skoda-Földes and Kollár et al The Heck reaction was used for the extension of the steroidal side chain by Pore et al [35] Rh-catalyzed hydroformylation of the unsaturated steroid D ring was carried out by Pereira and Banyón et al [36] [2+2+2] Cycloaddition Reactions Cycloadditions of unsaturated compounds catalyzed or mediated by transition metal complexes are powerful and efficient synthetic methods enabling the construction of cyclic systems in a single-step fashion. Usually, high levels of regio-and stereocontrol of these reactions, along with judicious choices of substitution patterns of the substrates in-volved, are translated into selective preparation of compounds with high levels of complexity.…”