QQ客服 官方微博 反馈留言

	脯氨酸的双功能催化作用对制备光学活性环型羟酮的机理研究; Mechanistic Study on Bffunctional Catalysis of Prolines in the Synthesis of Optically Active Cyclic Ketols
	叶秀林
	2001
关键词	脯氨酸 高脯氨酸 双功能催化作用 环型羟酮 praline homoproline bifunctional catalysis cyclic ketols
英文摘要	2-甲基-2-乙酰乙基-l,3-环戊二酮(1),在双功能催化剂L-(-)-脯氨酸的作用下,生成(+)-cis9S-羟基-8S-甲基氢茚-l,5-二酮[(+)-2],化学产率100%,光学纯度93.4%e.e.;而在L-(+)-高脯氨酸的作用下,得到的是(-)-2,产率73%,光学纯度65%e.e..另一方面,3R-(醛丙硫基)-4-硫杂环己酮可差同异构的衍生物(7)分别在D-或L-脯氨酸催化下,所得到的都是呈右旋光性的非对映立体异构的产物(+)-cis-1,8-二硫杂-4R-羟基-9R,10R-十氢萘-5-酮[(+)-8],但从D-脯氨酸得出的光学纯度高得多这些实验事实和反应机理均可以通过构象分析结合立体结构式得到合理的表达和解释.; It has been found that under the bifunctional catalysis of L-(-)-proline, 2-methyl-2-acetoethylcyclopentan-1,3-dione (1) cyclized to form (+)-cis-9S-hydroxy-8S-methylindan-1,5-dione [(+)-2] in 100% chemical yield and 93.4% e.e.; while under the catalysis of L-(+)-homoproline, 1 cyclized to form (-)-2 in 73% yield and 65% e.e.. On the other hand, under the catalysis of either D- or L- proline, the epimerizable diastereomer of 3R-(aldehydopropylmercapto)-4-thiacyclohexanone (7) cyclized to give dextro rotated diastereomeric product (+)-cis-1,8-dithia-4R-hydroxy-9R, 10R -decalin-5-one [(+)-8] in both cases. The catalysis by D-proline was noted to afford much better diastereoselectivity than that by L -proline. The above experimental results can be rationalized, as proposed in this article, by conformational analysis and by examining the conformation of transition state of the reactions expressed in three dimensional formulas.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000171884400028&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; SCI(E); 中文核心期刊要目总览(PKU); 中国科学引文数据库(CSCD); 0; 10; 1680-1685; 59
语种	中文
出处	万方 ; SCI ; http://d.g.wanfangdata.com.cn/Periodical_hxxb200110028.aspx
出版者	化学学报
内容类型	其他
源URL	[http://hdl.handle.net/20.500.11897/78469]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	叶秀林. 脯氨酸的双功能催化作用对制备光学活性环型羟酮的机理研究, Mechanistic Study on Bffunctional Catalysis of Prolines in the Synthesis of Optically Active Cyclic Ketols. 2001-01-01.

个性服务

查看访问统计

相关权益政策

暂无数据

收藏/分享

除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。