Asymmetric Total Synthesis of (-)-Azaspirene by Utilizing Ti-Claisen Condensation and Ti-Direct Aldol Reaction

被引：15
|
作者：
Sugi, Mikiko [1 ]
Nagase, Ryohei [1 ]
Misaki, Tomonori [2 ]
Nakatsuji, Hidefumi [1 ]
Tanabe, Yoo [1 ]
机构：
[1] Kwansei Gakuin Univ, Sch Sci & Technol, Dept Chem, 2-1 Gakuen, Sanda, Hyogo 6691337, Japan
[2] Univ Hyogo, Grad Sch Mat Sci, 3-2-1 Kohto, Kamigori, Hyogo 6781297, Japan
来源：
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 2016卷 / 28期
关键词：
Total synthesis; Asymmetric synthesis; Claisen condensation; Aldol reactions; Titanium; PSEUDEUROTIUM-OVALIS STOLK; PSEUROTIN-A; STEREOCONTROLLED SYNTHESIS; PRELIMINARY COMMUNICATION; DIECKMANN CONDENSATION; ANGIOGENESIS INHIBITOR; CHIRAL TEMPLATE; ACID-CHLORIDES; ROBUST METHOD; POWERFUL;
D O I：
10.1002/ejoc.201600766
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A successful asymmetric total synthesis of (-)-azaspirene has been accomplished by utilizing (3R)-6-cinnamyl-3-methyl-3-phenyl-1,4-dioxane-2,5-dione, a readily accessible chiral template. The present method involves two distinctive TiCl4/amine-mediated reactions: (i) an asymmetric Ti-crossed-Claisen condensation of the chiral template with propanoyl chloride followed by methanolysis to afford methyl (2R)-(4E)-2-hydroxy-5-phenyl-2-propanoylpent-4-enoate, the key chiral syn-thon and (ii) a robust Ti-direct aldol addition reaction, instead of the reported lithium diisopropylamide/hexamethylphosphorictriamide (LDA/HMPA) or potassium hexamethyldisilazide (KHMDS)-mediated reaction, by using the trimethylsilyl (TMS) ether of alpha-acyl-gamma-lactam to successfully furnish the new aldol adduct. Final oxidation, cyclization, and tert-butyldimethylsilyl (TBS) removal produced (-)-azaspirene from the key template in 23 steps (total yield 1.7 %).
引用
收藏
页码：4834 / 4841
页数：8
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