17-Thienyl-and 17-benzo[b]thienyl-3-hydroxyestra-1,3,5(10),16-tetraenes were synthesized by either sequential or one-pot Suzuki cross-coupling and Wittig olefination reactions. At 160 °C, heteroaryl substituted steroids were observed to undergo thermal intramolecular cyclization to produce E-ring heteroareno-annelated estranes.
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