Oh Hye Mi, Park Ji Eun, Kim Jisu, Kim Ju Hyun, Kang Youn K, Chung Young Keun
Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151-747 (Korea).
Chemistry. 2014 Jul 14;20(29):9024-36. doi: 10.1002/chem.201402087. Epub 2014 Jun 25.
A method for the synthesis of bicyclo[4.1.0]heptenes from 1,6-enynes through Pd-catalyzed cycloisomerization has been developed. N- and O-tethered 1,6-enynes were successfully transformed to their corresponding 3-aza- and 3-oxabicyclo[4.1.0]heptenes in reasonable-to-high yields using the catalysts [PdCl2(CH3CN)2]/P(OPh)3 or [Pd(maleimidate)2(PPh3)2] in toluene. The computational calculations using density functional theory indicate that [PdCl2{P(OPh)3}] in the oxidation state Pd(II) acts as the active catalyst species for the formation of 3-azabicyclo[4.1.0]heptenes through 6-endo-dig cyclization.
已经开发出一种通过钯催化的环异构化反应由1,6-烯炔合成双环[4.1.0]庚烯的方法。使用催化剂[PdCl2(CH3CN)2]/P(OPh)3或[Pd(马来酰亚胺)2(PPh3)2]，在甲苯中，N-和O-连接的1,6-烯炔成功地以中等至高收率转化为其相应的3-氮杂和3-氧杂双环[4.1.0]庚烯。使用密度泛函理论进行的计算表明，氧化态为Pd(II)的[PdCl2{P(OPh)3}]作为通过6-内型环化形成3-氮杂双环[4.1.0]庚烯的活性催化剂物种。
