Alkylation of enones via π-allyl complexes

C-5-Substituted pyrimidine nucleosides. 3. Reaction of allylic chlorides, alcohols, and acetates with pyrimidine nucleoside derived organopalladium intermediates

“…5-(3-Methyl-2-buten-l-yl)-2'-deoxyuridine (21) and 5-(3-Hydroxy-3-methyl-l-butyl)-2'-deoxyuridine (24) from the Reaction of 1 with 3-Acetoxy-3-methyl-1-butene. 5-(Chloromercuri)-2'-deoxyuridine (695 mg, 1.5 mmol) and 3-acetoxy-3-methyl-l-butene were reacted as outlined above in the preparation of 23.…”

“…The earlier eluting fraction (TLC Rf 0.34 (Q) was not identified. The later eluting fraction (TLC Rf 0.42 (C)) was evaporated to give 5-(3-hydroxy-3methyl-l-butyl)-2'-deoxyuridine (24): 45 mg (9.6% yield); XH NMR (100 MHz, D20) 7.70 (s, 1H), 6.35 (t, 1 H, J = 7 Hz), 4.46 (m, 1 ), 4.01 (m, 1 H), 3.83 (m, 2 H), 2.39 (m, 4 ), 1.70 (m, 2 ), 1.25 (s, 6 H); on being heated 24 softened at 80-85 °C and decomposed above 180 °C.…”

Synthesis of Transition-Metal Steroid Derivatives

“…In 1969, steroids 686g and 687 were also synthesized following an analogous pathway. 327 All these compounds were only partially characterized in these studies, and their stereochemistry was unambiguously established later on with X-ray diffraction studies of 686c 328 and 688. 329 A complete study based on deuterium-substituted steroids showed that formation of Pd π-allyl species arose from a loss of the 6βhydrogen, opposite to the metal approach.…”

“…In 1969, steroids 686g and 687 were also synthesized following an analogous pathway . All these compounds were only partially characterized in these studies, and their stereochemistry was unambiguously established later on with X-ray diffraction studies of 686c and 688 .…”