 用Zimmerman-Traxler六元環(huán)過(guò)渡態(tài)模型(J. Am. Chem. Soc. 1957, 79, 1920.)能夠較好的解釋說(shuō)明底物與產(chǎn)物立體化學(xué)見(jiàn)得關(guān)系。因?yàn)槿┑娜〈鵨quatorial處在平伏位置的過(guò)渡態(tài)穩(wěn)定，有烯醇的立體特異性決定產(chǎn)物的立體化學(xué)。也就是說(shuō)，由Z-烯醇鹽得到syn構(gòu)型羥醛產(chǎn)物、由E-烯醇鹽得到anti構(gòu)型產(chǎn)物。 一般而言，使用M-O鍵強(qiáng)的金屬（硬酸，絡(luò)合能較大的金屬）六元環(huán)過(guò)渡態(tài)的環(huán)足夠穩(wěn)固，立體選擇性會(huì)提高。加入HMPA等與鋰等金屬配位能力較強(qiáng)的配位性溶劑、可使金屬烯醇鹽得到極化，提高反應(yīng)性能。另一方面，因它不可能采取六元環(huán)過(guò)渡態(tài)，會(huì)使選擇性反轉(zhuǎn)，就變得依賴于底物。 反應(yīng)實(shí)例 【Tetrahedron 1997, 53, 9169-9202】 【J. Org. Chem. 2002, 67, 7750-7760】 【Org. Lett. 2003, 5, 733-736】 【Tetrahedron Lett. 1980, 21, 1031-1034】 【Angew. Chem. Int. Ed. 1997, 36, 166-168】 【J. Org. Chem. 2006,5228-5230】 【Eur. J. Org. Chem. 2008, 1759-1766】
【Angew. Chem. Int. Ed. 2008, 47, 6877-6880】
【Org. Lett. 2012, 14, 178-181】 1. Wurtz, C. A. Bull. Soc. Chim. Fr. 1872, 17, 436-442. Charles Adolphe Wurtz (1817-1884) was born in Strasbourg, France. After his doctoral training, he spent a year under Liebig in 1843. In 1874, Wurtz became the Chair of Organic Chemistry at the Sorbonne, where he educated many illustrous chemists such as Crafts, Fittig, Friedel, and van’t Hoff. The Wurtz reaction, where two alkyl halides are treated with sodium to form a new carbon-carbon bond, is no longer considered synthetically useful, although the aldol reaction that Wurtz discovered in 1872 has become a staple in organic synthesis. Alexander P. Borodin is also credited with the discovery of the aldol reaction together with Wurtz. In 1872 he announced to the Russian Chemical Society the discovery of a new by-product in aldehyde reactions with properties like that of an alcohol, and he noted similarities with compounds already discussed in publications by Wurtz from the same year. 2. Nielsen, A. T.; Houlihan, W. J. Org. React. 1968, 16, 1-438. (Review). 3. Still, W. C.; McDonald, J. H., III. Tetrahedron Lett. 1980, 21, 1031-1034. 4. Mukaiyama, T. Org. React. 1982, 28, 203-331. (Review). 5. Mukaiyama, T.; Kobayashi, S. Org. React. 1994, 46, 1-103. (Review on tin(II) enolates). 6. Johnson, J. S.; Evans, D. A. Acc. Chem. Res. 2000, 33, 325-335. (Review). 7. Denmark, S. E.; Stavenger, R. A. Acc. Chem. Res. 2000, 33, 432-440. (Review). 8. Yang, Z.; He, Y.; Vourloumis, D.; Vallberg, H.; Nicolaou, K. C. Angew. Chem. Int. Ed. 1997, 36, 166-168. 9. Mahrwald, R. (ed.) Modern Aldol Reactions, Wiley-VCH: Weinheim, Germany, 2004. (Book). 10. Desimoni, G.; Faita, G.; Piccinini, F.; Toscanini, M. Eur. J. Org. Chem. 2006,5228-5230. 11. Guillena, G.; Najera, C.; Ramon, D. J. Tetrahedron: Asymmetry 2007, 18, 2249-2293. (Review on enantioselective direct aldol reaction using organocatalysis.) 12. Doherty, S.; Knight, J. G.; McRae, A.; Harrington, R. W.; Clegg, W. Eur. J. Org. Chem. 2008, 1759-1766. 13. O’Brien, E. M.; Morgan, B. J.; Kozlowski, M. C. Angew. Chem. Int. Ed. 2008, 47, 6877-6880. 14. Trost, B. M.; Brindle, C. S. Chem. Soc. Rev. 2010, 39, 1600-1632. (Review). 15. Gazaille, J. A.; Abramite, J. A.; Sammakia, T. Org. Lett. 2012, 14, 178-181. 16. Esumi, T.; Yamamoto, C.; Tsugawa, Y.; Toyota, M.; Asakawa, Y.; Fukuyama Y. Org. Lett. 2013, 15, 1898–1901. 編輯自： 一、Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Aldol condensation，page 3-5. 二、Strategic Applications of Named Reactions in OrganicSynthesis, László Kürti and Barbara Czakó, aldol reaction, page 8-9. 三、化學(xué)空間：https://cn./reactions/%E5%8A%A0%E6%88%90%E5%8F%8D%E5%BA%94/2014/05/%E4%BA%A4%E5%8F%89%E7%BE%9F%E9%86%9B%E7%BC%A9%E5%90%88%E5%8F%8D%E5%BA%94cross-aldol-reaction.html 相關(guān)反應(yīng) |
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