中性加熱條件下吖丙啶基腙通過重氮中間體消除制備烯烴的反應(yīng)。產(chǎn)物為更多取代基的烯烴。利用BuLi作堿可以在低溫下進(jìn)行【J Am Chem Soc., 1980, 102, 774】。此反應(yīng)可以制備 Bamford-Stevens反應(yīng)和Shapiro反應(yīng)不能得到的三取代烯烴【Tet Lett., 1984, 25, 271】。
Rh2(OAc)4催化下，α-烯丙氧基酮腙通過Rh配位卡賓中間體得到Z-烯基烯丙氧醚，接著進(jìn)行Claisen重排得到反式二取代γ-不飽和酮或醛?！?em>J Am Chem Soc., 2002, 124, 12426】（7少畫了一個(gè)苯基，感謝葛樹升指正）
反應(yīng)操作
anti 2,3-Diphenyl-4-pentenal (10). To a Schlenk tube with Rh2(OAc)4 (2.5 mg, 0.0057 mmol) underN2 was added DCE (3 mL) and hydrazone 7 (101.9 mg, 0.277 mmol). The tube was sealed and the mixture was stirred at 130 ℃ till completion (TLC 18:1, pentane-ether) and passed through a silica pad and evaporated in vacuo. Flash chromatography (25:1, pentane-ether) gave 57 mg, 87% of 10, mp 101–103.5 ℃ (from pentane).
【J Am Chem Soc., 2002, 124, 12426】
相關(guān)文獻(xiàn)
1 Eschenmoser A Helv Chim Acta 1972 55 1276
2 Eschenmoser A Org Syn 1976 55 114
3 Evans DA J Am Chem Soc 1980 102 774
4 Collum DB Tet Lett 1984 25 271
5 Kirmse W Eur J Org Chem 1998 1 201
6 Stolz BM J Am Chem Soc 2002 124 12426
編譯自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, 141-142.
