金、銀催化1,3-環己雙烯苯行分子內hydroarylation環化反應

Abstract

利用(η5-1,3-環己雙烯) 或 (η5-1,3-環庚雙烯) 三羰鐵陽離子錯鹽，與sodium dimethylmalonate (丙二酸二甲酯鈉) 進行親核性反應，所得三羰鐵錯合物經硝酸鈰銨(CAN)氧化劑去錯合後，得到C-5位置帶有雙酯基之1,3-環己雙烯化合物與 1, 3-環庚雙烯化合物。將帶酯基之1,3-環形雙烯化合物在鹼性條件下與芳香環溴化物反應，可得C-5位置帶有雙酯基之1, 3-環形雙烯芳香環之衍生物。最後以金陽離子催化進行分子內 hydroarylation，可得到芳香環進行親核性加成的多環產物。 將帶酯基之1,3-環形雙烯化合物在鹼性條件下與3-溴丙炔反應，可得C-5位置帶有雙酯基之1,3-環形雙烯炔之化合物，以銀陽離子催化進行分子內環化反應，得到兩種不同位向選擇性的多環產物。另外，將帶酯基之1,3-環形雙烯化合物在鹼性條件下與2-溴甲基呋喃反應，可得C-5位置帶有雙酯基之1,3-環形雙烯呋喃之化合物。以銀陽離子催化會進行分子內Diels-Alder 反應，可以得到多環架橋化合物。

The addition of sodium dimethylmalonate to (η5-cyclohexa-1,3-diene) Fe(CO)3 or (η5-cyclohepta-1,3-diene) Fe(CO)3 cation followed by decomplexation with cerium ammonium nitrate (CAN) produced the C-5 diester substituted cyclic 1,3-dienes. The resulting diester dienes was treated with aryl- bromide in basic condition to generate aryl-substituted cyclohexa-1,3-diene or cyclohepta- 1,3-diene . Gold(I) catalyzed intramolecular hydroaryltion of aryl-substituted cyclo-1,3- diene produced hexahydrophenanthrene or cycloheptanaphthalene derivatives in good yields. The resulting diester dienes was treated with propayl-bromide in basic condition to generate cyclohexadienyne. Silver(I) catalyzed intramolecular cyclization of cyclohexa-1,3-dieyne produced two region isomers. Silver(I) catalyzed intramolecular Diels-Alder reaction of furan- substituted cyclohexa-1,3- diene produced bicyclo[2.2.2]octane derivative and tetrahydroacenaphthylene derivative in good yields.