銅催化下羧酸炔丙酯在強堿作用下生成端基丙二烯的反應(yīng)。另外在銅金屬催化劑、多聚甲醛、高位阻2級胺(二環(huán)己胺、二異丙胺等)存在下，末端炔烴也可以得到端基丙二烯。
Crabbe聯(lián)烯合成受限于多聚甲醛，其他醛不能生成聯(lián)烯。2010年麻生明及其研究團隊報道了新的合成方法，在廉價的的 ZnI2和嗎啡啉存在下，由醛和端基炔合成了1,3-二取代聯(lián)烯。
【Kuang, J.; Ma, S. J. Am. Chem. Soc. 2010, 132, 1786.】
反應(yīng)機理
端基炔和多聚甲醛反應(yīng)機理：
反應(yīng)實例
Allene (3). To PhSCu (4.41 g, 25.5 mmol) in Et2O (100 mL) at 35 C was added 2.47 M BuLi in hexane (9.91 mL, 2.45 mmol). After 20 min at -30 C, 1 (2.26 g, 10.2 mmol) in Et2O (35 mL) was added dropwise at -78 C. After 1 h stirring, the mixture was quenched with 2 mL of sat NH4Cl at a rate of 0.16 mL/min. After 6 h at 78 C, the solids were filtered at r.t.. The organic phase after washing, evaporation and chromatography afforded 1.51 g of 3 (91%).
【Normant JF, Tet Lett., 1976, 2313】
相關(guān)文獻
1 Crabbe′ P J Chem Soc Chem Comm 1976 183
2 Normant JF Tet Lett 1976 2313
3 Nantz MH Synthesis 1993 577
4 Hiemstra H J Org Chem 1997 62 8862
5 Takeda T Org Biomol Chem 2005 3 2914
6 Takahashi T J Org Chem 2005 70 8785
7 Crabbé, P.; Fillion, H.; André, D.; Luche, J.-L. J. Chem. Soc. Chem. Commun. 1979, 859.
8 Kuang, J.; Ma, S. J. Org. Chem. 2009, 74, 1763.
9 Kitagaki, S.; Komizu, M.; Mukai, C. Synlett 2011, 1129.
編譯自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 105.
