Heck reactions of steroidal alkenyl iodides.
Heck reactions of some steroid derivatives possessing iodo-alkenyl moiety (17-iodo-androst-16-ene, 1, 17-iodo-4-aza-4-methyl-androst-16-en-3-one, 2, 17-iodo-4-aza-androst-16-en-3-one, 3) were carried out in the presence of palladium catalysts using various olefins (methyl acrylate, ethyl methacrylate, allyl alcohol and allyl acetate) as coupling partners. With methyl acrylate, a side reaction was observed: the coupling product underwent a Diels-Alder reaction with the excess of methyl acrylate resulting in a six-membered carbocyclic E-ring. Reaction conditions of the synthesis of the Heck-product were optimized. Although the coupling with allyl alcohol led to the formation of 21-formyl-16-pregnene derivatives, the synthesis of the corresponding steroidal unsaturated alcohol could be achieved only via hydrolysis of the coupling product of the alkenyl iodide with allyl acetate.
Skoda-Földes
R
R
University of Veszprém, Department of Organic Chemistry, Hungary.
Bodnár
M
M
Kollár
L
L
Horváth
J
J
Tuba
Z
Z
D000179:Acrylates / Q000737:chemistry; D000475:Alkenes / Q000737:chemistry; D000736:Androstenes / Q000737:chemistry*; D007454:Iodides / Q000737:chemistry*; D008689:Methacrylates / Q000737:chemistry; D010165:Palladium / Q000737:chemistry; D020005:Propanols / Q000737:chemistry
D000179:Acrylates; D000475:Alkenes; D000736:Androstenes; D007454:Iodides; D008689:Methacrylates; D020005:Propanols; C000214:androst-16-en-3-one; C006463:allyl alcohol; D010165:Palladium; C035956:methyl acrylate