低价钛引起的(3-氧代-1,3-二芳基)丙基丙二腈的还原环化反应

Low valent Titanium Induced Reductive Cyclization of (3 Oxo 1,3 diaryl)propylpropanedinitrile

报道了低价钛试剂（ＴｉＣｌ４－Ｚｎ体系）与（３－氧代－１，３－二芳基）丙基丙二腈的反应．研究发现，低价钛可引起（３－氧代－１，３－二芳基）丙基丙二腈的成环反应，生成２－氰基－３，５－二芳基－１－氨基环戊烯、反式和顺式２－氨基－３－氰基－１，４－二芳基－２－环戊烯－１－醇３种产物，并用Ｘ射线衍射法确定了后两种异构体的构型．

This paper reports the reactions of low valent titanium reagent(TiCl 4 Zn system) with (3 oxo 1,3 diaryl) propylpropanedinitrile. It is found that the low valent titanium can promote a novel cyclization of (3 oxo 1,3 diaryl)propylpropanedinitrile to give 2 cyano 3,5 diary 1 aminocyclopentene, trans and cis 2 amino 3 cyano 1,4 diary 2 cyclopentene 1 ol. The latter's configurations are determinated by X ray diffraction analysis.The crystal of compound 3c is triclinic with space group P 1 , a =1.038 9(4) nm, b =1.229 2(4) nm, c = 0.802 7(3) nm, 7 α = 93.29(3)°, r =113.32(3)°, V =0.936 2(6) nm 3, Z =2, D c=1.193 9 g/cm 3, μ =0.77 cm -1 , F (000)= 360, and find R =0.067 and R w=0.057 for 130 8 reflections ( I >3 σ ( I )). The crystal of compound 4a is orthorhombic with space group Pbcn , a = 1.337 0(5) nm, b = 1.048 1(5) nm, c =2.335 0(6) nm, V =3.272(3) nm 3, Z =8, D c= 1.262 g/cm 3, μ = 2.36 cm -1 , F (000)=129 6, and find R =0.043 and R w=0.049 for 142 6 reflections ( I >3 σ ( I )). A possible reaction mechanism is proposed in this paper .