有机合成与诺贝尔奖2.pptVIP

Retrosynthetic tree 位置控制 保护基 活化基 桥连因子 Herbert C. Brown USA Purdue University West Lafayette, IN, USA 1912 - Georg Wittig Federal Republic of Germany University of Heidelberg Heidelberg, Germany 1897 - 1987 Boron compounds Herbert C Brown sodium boro-hydride(硼氢化钠) --the reagent of choice for reduction of carbonyl compounds Organoboranes(B2H6) (the most versatile reagents ever created in organic chemistry) can be used for reductions, rearrangements and additions and have opened up a range of new possibilities for linking carbon atoms to each other. 还原 重排 加成 Wittig reaction organic phosphorus compound with a formal double bond(含双键的有机磷化合物，双键在P和C之间) between phosphorus and carbon react with a carbonyl compound(羰基化合物). The oxygen of the carbonyl compound is exchanged for carbon, the product being an olefin(烯烃)。 芳基质子作为取代基的不稳定性 惊人发现：umpolung 规则 或极性逆转规则 F 的特异性 四烷基铵盐上的碳上的氢是否也有不稳定性？ 通过： 氯化四甲基铵 ylide N-ylide(氮叶立德) The semipolar nature of the N-C bond Its ability to add to benzophenone（二苯甲酮） P-ylide（磷叶立德） 应用：vitamin A的合成 硼也可以作为 tetracoordinate central atom 经证实，苯炔中间体存在的时间为：20 milliseconds. Thermal decomposition reactions used to determine the lifetime of dehydrobenzene in the gas phase 甲基锂 五甲基氮 失败！ Formation of Nylides Formation of P-ylides triphenylphosphinemethylene triphenylphosphineoxide 1，1-diphenylethylene Fig. 13. Steps in the reaction of triphenylphosphinemethylene with benzophenone 四元环过度态 * * Elias J. Corey －－Autobiography 1928 born in Methuen，Massachusetts 1944 entered M.I.T. 参与合成青霉素 1950 completed doctoral work joined University of Illinois 1956 became Professor of Chemistry 1959 work in Harvard 1957年 Elias J. Corey 提出了他的想法： The Logic of Chemical Synthesis retrosynthetic analysis 逆合成法 The logic of c