具方位與立體選擇性併苯乙醯基環戊烯酮與1,3-雙酮化合物的麥可加成反應

Regio-and Stereo-Selective Michael Addition of Acyl Indenone with 1,3-Diketones

柯鈞騰(Jiun-Teng Ke)

指導教授 ： 楊德芳

國立暨南國際大學/科技學院/應用化學學系/碩士(2019年)

https://doi.org/10.6837/ncnu201900023

摘要

參考本實驗室之前發表的成果，本研究利用1,3-茚滿二酮 7為起始物，透過dithiane的加成、水解、脫水反應，分別得到一系列3-(1,3-dithian-2-aryl)-3-hydroxy-indanone 114、3-acyl-3-hydroxy-indanone 116與acyl indenone 95衍生物。接著，透過1,3-diones 123對α,β-不飽和羰基系統之acyl indenone 95進行Michael addition形成富有區域選擇性之triacyl indanone 136，不僅產率最高可達97%，也有良好的單一非鏡像選擇性(dr>20:1)。然後透過NMR與X-ray單晶繞射等技術確定產物的相對立體結構。

關鍵字

併苯乙醯基環戊烯酮 ； 麥克加成 ； 非鏡像立體選擇性

並列摘要

In continuing the previous work of our lab, in this research, we used 1,3-indandione as a starting material, undergoing addition, hydrolysis and final dehydration to get a series of 3-(1,3-dithian-2-aryl)-3-hydroxy-indanone 114, 3-Acyl-3-hydroxy-indanone 116, Acyl-indenone 95 derivatives, respectively. Then, through Michael addition to α,β-unsaturated acyl-indenone 95 with 1,3-diones 123 and TMEDA as catalyst, the reaction proceeded in toluene at 30 oC, giving the regioselective-rich triacyl indanones 136 with good yield (up to 97%) and high diastereoselectivity (up to 20:1 dr). The relative stereo-structure of products were confirmed by NMR technique and X-ray crystallography.

並列關鍵字

Acyl-indenone ； Michael addition ； diastereoselectivity

參考文獻

參考文獻

1. Nagao, Y.; Jeong, Y.; Lee, W. -S.; Goto, S.; Sano, S.; Shiro, M. Tetrahedron.1998, 54, 14437.

2. Meng, J. -B.; Han, J.; Wang, C. -Q.; Wei, Y. -H.; Pang, M. -L. Chin. J. Chem. 2008, 26, 765.

3. Qin, Z.; Xiao, Y.; Han, X.; Wan, X.; Li, X.; Li, H.; Y, D.; Du, S. Bioorg. Med. Chem. Lett. 2015, 25, 2438.

4. Corey, E. J,; Erickson, B. W. J. Org. Chem. 1971, 36, 3553.