Colvin炔合成反应

醛酮和LiTMSD（三甲基硅基重氮甲烷锂盐）反应后，接着消除（Peterson烯合成 ）脱氮气得到卡宾，重排生成多一个碳的炔烃的反应。反应中的卡宾重排类似Fritsch–Buttenberg–Wiechell重排反应。

环酮可以通过此反应扩环得到多一个碳的环炔类化合物。

反应机理

反应实例

p-Methoxyphenylpropyne (4). To LDA in THF (8 mL) was added trimethylsilyldiazomethane 2 (1.9 M in hexane, 0.63 mL, 1.2 mmol) at -78 C under Ar. After 30 min, ketone 1 (150 mg, 1 mmol) in THF (2 mL) was added dropwise at 78 C. After 1 h the mixture was refluxed for 3 h, quenched

(H2O) and extracted with Et2O. Evaporation and chromatography provided 199.7 mg of 4 (82%), bp 85–88 C/0.9 mm.

【Aoyama T, Shiori T, Tet Lett, 1994, 35, 107】

相关文献

1 Colvin EV J Chem Soc Chem Comm 1973 151

2 Colvin EV J Chem Soc Perkin Trans 1 1977 869

3 Colvin EV J Chem Soc Chem Comm 1992 721

4 Aoyama T, Shiori T Tet Lett 1994 35 107

5 Roth GJ Synthesis 2004 59

6 Mulzer J Angew Chem Int 2009 48 6032

编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 93.