Hanaoka-Wrobel喹诺里西啶合成
喹诺里西啶（Quinolizidine ）
碱催化下异石榴皮碱（2-丙酮基哌啶）和芳醛缩合得到喹诺里西啶酮的反应。通常用氢氧化钠催化下反式构型产物（3）是主要产物。此反应是非常重要的合成生物碱的方法。
反应机理
反应机理由两种可能：1、芳醛和酮进行羟醛缩合后消除得到α，β-不饱和酮，接着进行Michael加成得到产物。2、直接进行Mannich反应得到产物。
反应操作
trans- and cis-4-Phenyl-2-quinolizidinone (3 and 4). 6N aq NaOH (1 mL) was added to distilled benzaldehyde 2 (143 mg, 1.35 mmol) and 1 (146 mg, 1.03 mmol) in 10 mL MeOH and the mixture was stirred for 3 h at 55 C. After evaporation, the residue was diluted with brine and extracted with CHCl3. Usual workup and preparative layer chromatography (silica gel, PhH:ether 5:1) gave 81 mg (34%) of 3 (from band Rf = 0.2, PhH:EA 1:1), and 61 mg (26% yield) of 4 (from band Rf = 0.5). Recrystallization of 4 from hexane, mp 64 C.
【Quick J, J Org Chem., 1979, 44, 573】
相关文献
1 Wrobel JT Rocz Chem 1971 45 705
2 Hanaoka M Chem Pharm Bull 1974 22 1945
3 Hanaoka M Chem Pharm Bull 1975 23 1573
4 Wrobel JT Bull Acad Pol Sci (Chim) 1975 23 593
5 Quick J J Org Chem 1979 44 573
6 Carter RG J Org Chem 2008 73 5155
编译自：Organic Syntheses Based On Name Reactions, 3RdEd, A. Hassner, Page 201.
相关文章