Copper(I)- and Copper(II)-catalyzedDiels-Alder Additions of ?-Substituted Acrylonitrile to Furan. The Synthesis of 7-Oxa-bicyclo[2.2.1]hept-5-en-2-one
作者:Eric Vieira、Pierre Vogel
DOI:10.1002/hlca.19820650604
日期:1982.9.22
The difficult Diels-Alder additions of α-acetoxy- and α-chloroacrylonitrile to furan can be run at 20–35° and atmospheric pressure in the presence of CuCl. Cu(BF4) · 6 H2O, Cu(OOCCH3)2 · H2O or cupric tartrate · 3H2O. Under kinetic control, the exo-carbonitrile adducts 2 and 8, respectively, are favoured. Saponification of the 2endo-acetoxy-7-oxabicyclo[2.2.1]hept-5-ene-2exo-carbonitrile (2) furnished
在CuCl存在下,难以在Diels - Alder中向呋喃中添加α-乙酰氧基和α-氯丙烯腈的方法是在20–35°和大气压下进行。的Cu(BF 4)·6 H 2 O,的Cu(OOCCH 3)2 ·H 2 O或酒石酸铜·3H 2 O.在动力学控制,所述外腈加合物2和8分别被青睐。所述的皂化2endo乙酰氧基-7-氧杂双环[2.2.1]庚-5-烯-2-外-甲腈(2)提供的7-氧杂二环[2.2.1]庚-5-烯-2-酮(4)。α-氯丙烯腈加合物(8 + 9)水解成呋喃及其5 exo,6 exo-异丙基二烯二氧基衍生物的碱性水解未得到相应的酮,分离出羧酰胺14 + 15和16 + 17。