Synthesis of novel chiral bisoxazoline ligands with a spiro[4,4]-1,6-nonadiene skeleton  

作　　者：HAN ZhaoBin WANG Zheng ZHANG XuMu DING KuiLing 

机构地区：[1]State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China [2]Department of Chemistry and Chemical Biology, Center of Molecular Catalysis, Rutgers, The State University of New Jersey, New Jersey 08854-8066, USA

出　　处：《Chinese Science Bulletin》2010年第25期2840-2846,共7页

基　　金：supported by the National Natural Science Foundation of China (20821002 and 20972176);the Chinese Academy of Sciences, the National Basic Research Program of China (2010CB833300),the Science and Technology Commission of Shanghai Municipality,and Merck Research Laboratories

摘　　要：A new type of chiral bisoxazoline ligands 1 based on spiro[4,4]-1,6-nonadiene backbone was easily prepared in six steps from racemic spiro[4,4]-nonane-1,6-dione,with the Pd-catalyzed coupling of the enol triflates with CO and amino alcohols as the key steps for the construction of the oxazoline moiety. The structure of the ligand (R,S,S)-1b was unambiguously established by X-ray crystallographic analysis. The chiral Cu(II) complex generated in situ from the combination of spiro bisoxazoline ligand (S,S,S)-1c and Cu(OTf)2 was effective in the catalysis of asymmetric chlorination of the β-ketoester,methyl 1-oxo-2,3-dihydro-1H-indene-2-carboxylate,affording the corresponding chlorinated derivative in 99% yield with 17% ee.A new type of chiral bisoxazoline ligands 1 based on spiro[4,4]-1,6-nonadiene backbone was easily prepared in six steps from racemic spiro[4,4]-nonane-1,6-dione, with the Pd-catalyzed coupling of the enol triflates with CO and amino alcohols as the key steps for the construction of the oxazoline moiety. The structure of the ligand （R,S,S）-1b was unambiguously established by X-ray crystallographic analysis. The chiral Cu（II） complex generated in situ from the combination of spiro bisoxazoline ligand （S,S,S）- lc and Cu（OTf）2 was effective in the catalysis of asymmetric chlorination of the β-ketoester, methyl 1-oxo-2,3-dihydro-lH- in- dene-2-carboxylate, affording the corresponding chlorinated derivative in 99% yield with 17% ee.

关 键 词：双恶唑啉 配体 手性 铜(Ⅱ)配合物 X射线晶体分析 螺 合成 骨架 

分 类 号：O633.14[理学—高分子化学] O641.4[理学—化学]