Diisopropyltren was synthesized from the reaction of tren with benzaldehyde in toluene, followed by reducing the imine intermediate with NaBH4, and debenzylation catalyzed by 10% Pd/C in methanol. It was then converte...Diisopropyltren was synthesized from the reaction of tren with benzaldehyde in toluene, followed by reducing the imine intermediate with NaBH4, and debenzylation catalyzed by 10% Pd/C in methanol. It was then converted to its corresponding azaphosphatrane via ring-closing reaction of HMPT and triflic acid. Deprotonation of azaphosphatrane with potassium t-butoxide afforded the target diisopropyl proazaphosphatrane ld. A comparative study of compound ld for isomerization of allylic system and methylene-interrupted diene system revealed that compound ld is more efficient than its tri-substituted analoque（lb）. In acetonitrile at 40 ℃, allylaromatics were selectively isomerized to 1-arylpropene generally in an isolated yield more than 95% with trans, cis molar ratios in a range of 87/13 to 96/4. Allyl phenylsulfide was converted to 1-phenylthiopropene（molar ratio of Z/E=54/46） in a yield of 93%-95%. Methylene-interrupted dienes were also isomerized in high yield.展开更多
基金Supported by the Natural Science Foundation of Shandong Province, China(No.Y2007F05)
文摘Diisopropyltren was synthesized from the reaction of tren with benzaldehyde in toluene, followed by reducing the imine intermediate with NaBH4, and debenzylation catalyzed by 10% Pd/C in methanol. It was then converted to its corresponding azaphosphatrane via ring-closing reaction of HMPT and triflic acid. Deprotonation of azaphosphatrane with potassium t-butoxide afforded the target diisopropyl proazaphosphatrane ld. A comparative study of compound ld for isomerization of allylic system and methylene-interrupted diene system revealed that compound ld is more efficient than its tri-substituted analoque（lb）. In acetonitrile at 40 ℃, allylaromatics were selectively isomerized to 1-arylpropene generally in an isolated yield more than 95% with trans, cis molar ratios in a range of 87/13 to 96/4. Allyl phenylsulfide was converted to 1-phenylthiopropene（molar ratio of Z/E=54/46） in a yield of 93%-95%. Methylene-interrupted dienes were also isomerized in high yield.
