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

1.通过自由基级联反应，芳基在烯酰胺的烯键上6-内选择性环化，生成的酰胺基5-内环化，方便地合成了C13位含甲基的菲并吲哚里嗪.自由基级联反应包括烯酰胺烯键上的烷基6-内选择性环化和生成的酰胺基5-内环化，提供了一种方便的合成柱孢菌素的方法.通过自由基级联反应，芳基与烯酰胺的烯键7-内选择性环合，再与酰胺基5-内环合，得到了一种简便的合成头孢菌素的新方法.通过自由基级联反应，芳基在烯酰胺的烯键上7-内选择性环化，得到酰胺基的均裂芳香取代，得到了一个简短的lennoxamine的合成.自由基级联反应包括烯酰胺烯键上的烷基7-内选择性环化和所得酰胺基的5-内环化，得到了百部酰胺、异百部酰胺、百部胺和异百部胺的全合成. 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，进行自由基环化反应，得到相应的γ-内酰胺。本文详细研究了烯酰胺中芳基或烷基对烯键的外型和内型选择性。

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.