在Ti催化下格氏試劑和烯烴或炔烴進(jìn)行交換得到新的格氏試劑，再和一些親電試劑（氧氣，二氧化碳，醛，腈等等）進(jìn)行格氏反應(yīng)。端基硅保護(hù)的炔丙醇和腈發(fā)生此反應(yīng)可以制備各種取代呋喃。
反應(yīng)機(jī)理
反應(yīng)實(shí)例
β-(Cyclohexenyl)ethanol (3). To 1, prepared from Mg (13.2 g) and PrBr (61.3 g) in Et2O (150 mL), was added 2 (54 g, 0.5 mol) followed by TiCl4 (1 mL). After 2 h reflux and heating with more TiCl4 (0.5 mL), the mixture was oxidized with air and distilled to give 25 g of 3 (40%), bp 92–94 ℃.
【Cooper GD, Finkbeiner HL, J Org Chem., 1962, 27, 3395】
3-Trimethylsilyl-2-ethylfuran (6). Cp2TiCl2 (0.12 g, 0.48 mol) was added to i-BuMgBr in Et2O (43 mL, 0.4 M) under Ar at 0℃. 4 (0.18 g, 6.8 mmol) was added and the mixture was stirred for 6 h at r.t. EtCN (0.48 g, 8.8 mmol) was added and all was stirred for another 2 h at r.t. Workup and chromatography (silica gel) afforded 0.94 g of 6 (82%).
【Sato F, Tet Lett., 1984, 25, 5063】
【Tet Lett., 1993, 34, 4975-4978】
相關(guān)文獻(xiàn)
1 Cooper GD, Finkbeiner HL J Org Chem 1962 27 3395
2 Sato F J Chem Soc Chem Comm 1981 718
3 Sato F Tet Lett 1983 24 1804
4 Sato F J Chem Soc Chem Comm 1983 162
5 Sato F Tet Lett 1984 25 5063
6 Adam W Synthesis 1994 567
7 Wolan A Tetrahedron 2010 66 15
參考文獻(xiàn)
一、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 96.
二、Reactionflash APP
