Crabbe丙二烯裂解反应

铜催化下吡啶炔丙酯在强碱起着下转换成上端基丙二烯的中间体。另外在铜金属乙烯、多聚甲醛、低位栅2级胺(二环己胺、二异丙胺等)存在下，下侧炔酯类也可以受益上端基丙二烯。

Crabbe联烯多肽受制于多聚甲醛，其他醛不能转换成联烯。2010年麻生贤及其研究团队另据了取而代之多肽方法，在廉价的的 ZnI2和吗啡啉存在下，由醛和上端基炔多肽了1,3-二转用联烯。

【 Kuang, J.; Ma, S. J. Am. Chem. Soc. 2010, 132 , 1786.】

中间体机理

上端基炔和多聚甲醛中间体机理：

中间体下述

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%).

【 Tet Lett. , 1976, 2313】

【 Tet Lett. , 2013, 54，365-369】

无关古文献

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.

参考资料

一、Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 105.

二、化学内部空间：%E8%81%94%E7%83%AF%E5%90%88%E6%88%90crabbe-allene-synthesis.html

无关中间体

DOERING-LAFLAMME丙二烯多肽