含面手性、膦手性和碳中心手性二茂铁氨基烷基膦中间体的高效合成  

Efficient synthesis of planar,phosphine and carbon-centered chiral ferrocenyl aminoalkyl phosphine intermediates

作　　者：朱澳平 郭强 姜军 王凯[1] ZHU Aoping;GUO Qiang;JIANG Jun;WANG Kai(College of Health Science and Engineering,Hubei University,Wuhan 430062,China;Yichang Chengkai Chemical Technology Co.,Ltd.,Yichang 443000,China)

机构地区：[1]湖北大学健康科学与工程学院,湖北武汉430062 [2]宜昌诚凯化工科技有限公司,湖北宜昌443000

出　　处：《湖北大学学报(自然科学版)》2025年第3期434-440,共7页Journal of Hubei University:Natural Science

基　　金：湖北省自然科学基金(2018CFB307);湖北省功能化学品工程技术研究中心开放基金(GCZX-2022-07)资助。

摘　　要：含有面手性及碳中心手性的二茂铁氨基膦中间体在不对称催化中被广泛运用,然而其结构仍然局限。目前报道的这类化合物膦原子上通常为芳基,缺乏烷基膦中间体的报道,同时也缺乏含有膦手性的该类中间体的相关报道,这主要是受限于这类化合物合成上的挑战性。含有面手性的二茂铁氨基膦化合物的合成需要通过稳定性较差的醋酸酯中间体与氨水在两相溶液中于高温下反应,但是醋酸酯中间体在高温下易于消除,同时由于反应液为非均相,反应收率较低,该方法通常不适用于二茂铁氨基烷基膦中间体的合成。本研究针对这一难题,发展了该类中间体的高效合成方法,并合成了几类新型同时含面手性、膦手性和碳中心手性的二茂铁氨基烷基膦中间体。基于新合成的中间体,本研究同时合成了新型膦手性二茂铁硫脲配体。Ferrocenyl aminophosphine intermediates with planar and carbon centered chirality have been widely used in asymmetric catalysis.However,their structures diversity is limited.At present,such compounds reported are usually those with aryl groups on the phosphine atom,and there is a lack of alkyl phosphine intermediates,as well as the lack of intermediates with phosphine chirality,mainly due to the challenges in the synthesis of such compounds.The synthesis of ferrocenyl aminophosphine compounds containing planar chirality requires the reaction of acetate intermediates with ammonia in a two-phase solution at high temperature through a poorly stable acetate intermediate.Since the acetate intermediate is easy to eliminate at the high temperature and the reaction solution is not homogeneous,the reaction yield is low.The existing method is usually not suitable for the synthesis of ferrocenyl aminoalkyl phosphine intermediates.In order to address this problem,an efficient synthesis method for these intermediates was developed,and several novel intermediates containing planar chirality,phosphine chirality and carbon centered chirality were synthesized.Based on the newly synthesized intermediates,a new phosphine chiral ferrocenyl thiourea ligand was synthesized.

关 键 词：面手性 膦手性 碳中心手性 二茂铁氨基膦中间体 二茂铁硫脲配体 

分 类 号：O622.6[理学—有机化学]