The Cobalt-Mediated [2+2+2] Cycloaddition of α,ω-Diynes to the 2,3-Double Bond of Indole
作者:Roland Boese、Andrew P. Van Sickle、K. Peter C. Vollhardt
DOI:10.1055/s-1994-25696
日期:——
The reaction of acetyl or phenylsulfonylindole with α,Ï-diynes and CpCo(C2H4)2 yields CpCo-complexed dihydrocarbazoles. 1-Trimethylsilyl-1,6-heptadiyne gives an adduct in which the silyl moiety is distal to the phenylsulfonamide. 1-Trimethylsilyl-1-7-octadiyne results in an unusual diene complex resulting from C-H activation at C-2 of the indole. The behavior of a number of terminally substituted 4-aza-1,7-octadiynes to the reaction is investigated. The oxidation of one dihydrocarbazole complex with triphenylcarbenium hexafluorophosphate or with Fe(NO3)3 furnishes an η5-cyclohexadienyl cobalt complex and its subsequent conversion into substituted diene complexes or to the demetallated carbazole is discussed.
乙酰基或苯磺酰基吲哚与 δ、Ï-二炔和 CpCo(C2H4)2 反应生成 CpCo 复合物二氢咔唑。 1-三甲基硅基-1,6-庚二炔生成的加合物中,硅基位于苯磺酰胺的远端。1-Trimethylsilyl-1,7-octadiyne 产生了一种不寻常的二烯复合物,这是由于吲哚的 C-2 处发生了 C-H 活化。研究了一些末端取代的 4-氮杂-1,7-辛二炔在反应中的行为。讨论了一种二氢咔唑络合物与六氟磷酸盐三苯基羰基或与 Fe(NO3)3 的氧化反应生成的 Î-5-cyclohexadienyl 钴络合物及其随后转化为取代的二烯络合物或脱金属咔唑的情况。