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

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分类：O633.14[理学—高分子化学;理学—化学] O641.4[理学—物理化学;理学—化学]
作者机构：[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
相关基金：This paper is dedicated to Professor LIU YouCheng on the occasion of his 90th birthday. This work was 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 is gratefully acknowledged.

作者： HAN ZhaoBin[1], WANG Zheng[1], ZHANG XuMu[1,2], DING KuiLing[1]

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, spiro ligand, bisoxazoline, asymmetric chlorination, β-ketoester

中文摘要：

chiral bisoxazoline ligands 的一种新类型 1 基于 spiro [4,4 ]-1,6-nonadiene 脊梁容易从外消旋的 spiro 在六步被准备[4,4 ] 有作为钥匙的与公司和氨基的白酒的 enol triflates 的催化 Pd 的联合的 -nonane-1,6-dione, 为 oxazoline 一半的构造走。ligand 的结构(R， S， S )-1b 被 X 光检查结晶的分析明白地建立。从 spiro bisoxazoline ligand 的联合在 situ 产生的 chiral Cu ( II )建筑群( S ， S ， S ) -1c 和 Cu ( OTf ) 2 在-ketoester,甲基1-oxo-2,3-dihydro-1H- indene-2-carboxylate 的不对称的氯化的催化作用是有效的，与17% ee 在99%产量负担得起相应使氯化的衍生物。

英文摘要：

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）- 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.