Deve I opment of Practical Radical Reaction and its Applicat i on to the Synthesis of Physiologically Active Compounds

1. 自由基级联反应包括芳基自由基在烯酰胺键上的6端选择性环化，以及由此产生的酰胺基自由基的5端环化，从而方便地合成了在C13位置上含有甲基的吩anthroindolizidines。自由基级联反应包括烷基自由基在酰胺烯烃键上的6端选择性环化和由此产生的酰胺基自由基的5端环化，为圆柱骨架的合成提供了方便。自由基级联反应包括芳基自由基在烯酰胺键上的7端选择性环化，以及由此产生的酰胺基自由基的5端环化，从而简明地合成了脑毒素骨架。自由基级联反应是将芳基自由基7位选择性环化到烯酰胺的烯烃键上，并将所得到的酰胺基自由基均溶芳取代，从而在短时间内合成了苯诺克胺。自由基级联反应包括烷基自由基在酰胺的烯烃键上的7-内环选择性环化，以及由此产生的酰胺基自由基的5-内环化，从而合成了系统胺、异系统胺、系统胺和异系统胺。n -烯丙基或n -乙烯基，α, α， α-三氯乙酰胺在1,4 -二甲基哌嗪中加热后，发生自由基环化反应，得到相应的y-内酰胺。详细研究了芳基和烷基自由基对烯键的外、内选择性。

1. Radical cascade involving 6-endo selective cyclization of aryl radical onto olefinic bond of enamide and 5-endo cyclization of the resulting amidoyl radical afforded a convenient synthesis of phenanthroindolizidines containing a methyl group at their C13 position.2. Radical cascade involving 6-endo selective cyclization of alkyl radical onto olefinic bond of enamide and 5-endo cyclization of the resulting amidoyl radical afforded a convenient synthesis of cylindricine skeleton.3. Radical cascade involving 7-endo selective cyclization of aryl radical onto olefinic bond of enamide and 5-endo cyclization of the resulting amidoyl radical afforded a concise synthesis of cephalotoxine skeleton.4. Radical cascade involving 7-endo selective cyclization of aryl radical onto olefinic bond of enamide and homolytic aromatic substitution of the resulting amidoyl radical afforded a short synthesis of lennoxamine.5. Radical cascade involving 7-endo selective cyclization of alkyl radical onto olefinic bond of enamide and 5--endo cyclization of the resulting amidoyl radical afforded a total synthesis of stemonamide, isostemonamide, stemonamine, and isostemonamine.6. N-Allylic or N-vinylic, α, α, α-trichloroacetamides, upon heating in 1, 4-dimethylpiperazine, underwent radical cyclization to give the corresponding y-lactams.7. exo and endo Selectivities of aryl or alkyl radical onto olefinic bond of enamides were studied in detail.