有机化学及实验教学课件全套-有机合成与诺贝尔奖-考研试题文档资料系列.ppt

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1、 Elias J. Corey Autobiography 1928born in Methuen，Massachusetts 1944entered M.I.T.参与合成青霉素参与合成青霉素 1950 completed doctoral work joined University of Illinois 1956became 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

2、逆合成法The logic of chemical synthesis简单的原料简单的原料 复杂的分子复杂的分子 transformsynthesis反合成分析法反合成分析法retrosynthetic analysis retrosynthetic analysisRetrosynthetic tree树根目标分子树根目标分子树枝原料树枝原料Best Choice?位置控制 保护基活化基 桥连因子To build left- or right handed molecules Herbert C. Brown USA Purdue University West Lafayette, IN,

3、 USA 1912 - Georg Wittig Federal Republic of Germany University of Heidelberg Heidelberg, Germany 1897 - 1987 The Nobel Prize in Chemistry 1979Laureates: Herbert C. Brown Georg Wittig for their development of the use of boron- and phosphorus-containing compounds, respectively, into important reagent

4、s in organic synthesisBoron compoundsHerbert C Brownsodium 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)OCRRNaBH4CHRROHHHHCH3B2H6+HHCHHCH3 3Bcan be used for reductions, rearrangements

5、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 comp

6、ound is exchanged for carbon, the product being an olefin(烯烃)。(C6H5)3P=CH2+R2C=O(C6H5)3P=O+R2C=CH2 这是我们熟悉的Wittig试剂，用于双键化合物的制备A carbonyl compound(羰基化合物)organic phosphorus compound with a formal double bondbetween phosphorus and carbonolefin(烯烃)Fig. 1. Formation of a diradical被削弱的C-C键demetalization 有机

7、金属锂化合物 diradicalFormation and characterization of compound 9zinc dust distillation.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Reversal of polarity (umpolung) 极性逆转极性逆转Mechanism of formation of o-lithiobiphenylProof of the intermediate occurrence of dehydrobenzene in the reaction of 14 C-labeled chlo

8、robenzene with potassium amide in liquid ammoniaFig. 8. Proof of the existence of dehydrobenzene through the formation of 10苯炔中间体存在的证实：在反应过程中加入二烯体呋喃，分离出产物10a Diels-Alder addition：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

9、gas phase 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 甲基锂 五甲基氮 失败！Formation of Nylidesylide CXFormation of P-ylidesN-ylide(氮叶立德)The semipolar nature of the N-C bondIts ability to add to benzophenone（二苯甲酮）P-ylide（磷叶立德）triphenylphosphinemethylenetriphenylphosphineoxide1，1-diphenylethylene Fig. 13. Steps in the rea

10、ction of triphenylphosphinemethylene with benzophenone 四元环过度态应用：vitamin A的合成硼也可以作为 tetracoordinate central atom参考文献E.J. Corey, X.-M. Cheng: The Logic of Chemical Synthesis, Wiley Interscience, 1989.E.J. Corey, A.K. Long, S.D. Rubenstein: Computer-Assisted Analysis in Organic Synthesis, Science, Vol

11、228, 1985, pp 408-418. The Royal Swedish Academy of Sciences, Information about the Nobel Prize in Chemistry 1990 (press release). Further readingG. Wittig and M. Rieber, ibid. 562, 187 (1949).G. Wittig and K Clauss, ibid. 577, 26 (1952); ibid. 578,136 (1952).G. Wittig and K. Torssell, Acta Chem. Stand. 7, 1293 (1953).H. Pommer, Angew. Chem. 89,437 (1977).R. W. Hoffmann, Dehydrobenzae and Cycloalkynes (Academic Press, New York, 1967).有机合成设计 英 S 特纳 化学工业出版社叶立德化学 黄文芳 华中师范大学出版社极性转换及其在有机合成中的应用 刘志昌 科学出版社