Catalytic Enantioselective Amide Allylation of Isatins and Its Application in the Synthesis of 2-Oxindole Derivatives Spiro-Fused to the α-Methylene-γ-Butyrolactone Functionality

被引:47
作者
Takahashi, Masaki [1 ]
Murata, Yusuke [2 ]
Yagishita, Fumitoshi [3 ]
Sakamoto, Masami [3 ]
Sengoku, Tetsuya [1 ]
Yoda, Hidemi [1 ,2 ]
机构
[1] Shizuoka Univ, Grad Sch Engn, Naka Ku, Hamamatsu, Shizuoka 4328561, Japan
[2] Shizuoka Univ, Grad Sch Sci & Technol, Naka Ku, Hamamatsu, Shizuoka 4328561, Japan
[3] Chiba Univ, Dept Appl Chem & Biotechnol, Grad Sch Engn, Inage Ku, Chiba 2638522, Japan
关键词
allylation; antitumor agents; asymmetric catalysis; lactones; spiro compounds; SESQUITERPENE LACTONES; ASYMMETRIC-SYNTHESIS; STEREOSELECTIVE-SYNTHESIS; N-IODOSUCCINIMIDE; ALDEHYDES; OXINDOLES; SPIROOXINDOLES; ALLYLSTANNANES; ALLYLSILANES; CONSTRUCTION;
D O I
10.1002/chem.201403357
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
This article is a full account of the work exploring the potential utility of catalytic enantioselective amide allylation of various isatins using indium-based chiral catalysts. A survey of various isatin substrates and NH-containing stannylated reagents revealed that the reaction has a remarkably wide scope to result in extremely high yields and enantioselectivities (up to > 99 %, 99% ee) of variously substituted homoallylic alcohols. Several mechanistic investigations demonstrated that the substrate-reagent hydrogen-bond inter-action plays a critical role in the formation of the key transition states to result in enhanced catalytic reaction. The success of this approach allowed convenient access to chiral 2-oxindoles spiro-fused to the alpha-methylene-gamma-butyrolactone functionality and their halogenated derivatives in almost enantiopure forms, thus highlighting the general utility of this synthetic method to deliver a large variety of antineoplastic drug candidates and pharmaceutically meaningful compounds.
引用
收藏
页码:11091 / 11100
页数:10
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