Stereoselective Synthesis of Steroids with the Heck Reaction

Abstract

By means of a double Heck reaction the pharmacologically interesting estrapentaene 3 can be synthesized regio‐ and stereoselectively from (Z)‐(2‐bromoethenyl)‐bromobenzene (1) and the indene derivative 2. A variety of novel steroids can be obtained by variation of the benzene and indene components and subsequent functionalization.

Regioselective palladium-catalysed cross-coupling reactions: a powerful synthetic tool

“…Recently, Tietze and coworkers with the aim of developing shorter and efficient synthetic routes for accessing steroidal molecules (Estrone derivative, 21), carried out a step-wise double Heck reaction between (Z)-(2-bromoethenyl)bromobenzene and hexahydro-1H-indene derivative (Scheme 20). 83 One of the key features of the protocol was the highly regio-and stereoselective Heck reaction with the C-C bond formation taking place anti to the angular methyl group. This step was then followed by another ring closing intramolecular Heck reaction affording the Scheme 18 (+)-g-Lycorane (18) synthesis via regio-and enantioselective allylation reaction.…”

Phospha-palladacycles and N-heterocyclic carbene palladium complexes: efficient catalysts for CC-coupling reactions

“…Scientific and industrial applications of Heck reactions catalyzed by palladacycle 1a have been reported for the total synthesis of estrone steroid derivatives [29], the anti-leukaemia alkaloid cephalotoxin [30]. The vinylation of 2-bromo-6-methoxynaphthalene with ethylene to a single product [31] has been applied on the pilot plant-scale for the synthesis of Naproxen by Hoechst (Scheme 4).…”

Stereoselective Synthesis of Novel 19-Nor-Steroids by a Double Heck Reaction

“…[11] However, a total synthetic approach is indispensable in order to gain access to analogs that cannot be derived from natural steroids. [14,15] A similar approach has also been successfully employed in the synthesis of -homoestradiols [16] and novel aza-heterocycles. [14,15] A similar approach has also been successfully employed in the synthesis of -homoestradiols [16] and novel aza-heterocycles.…”