中国科学院上海有机化学研究所机构知识库
Advanced  
SIOC OpenIR  > 中科院有机氟化学重点实验室  > 期刊论文
学科主题: 氟化学
题名: Nucleophilic fluoroalkylation of alpha,beta-enones, arynes, and activated alkynes with fluorinated sulfones: Probing the hard/soft nature of fluorinated carbanions
其他题名: Nucleophilic fluoroalkylation of alpha,beta-enones, arynes, and activated alkynes with fluorinated sulfones: Probing the hard/soft nature of fluorinated carbanions
作者: Ni CF(倪传法) ; Zhang LJ(张来俊) ; Hu JB(胡金波)
通讯作者: 胡金波
刊名: J. Org. Chem.
发表日期: 2008-01-01
卷: 73, 期:15, 页:5699-5713
收录类别: SCI
部门归属: 中科院上海有机所
英文摘要: We have successfully accomplished the nucleophilic fluoroalkylation of alpha,beta-enones, arynes, and activated alkynes with fluorinated sulfones. It was found that for acylic (x,,3-enones, although the reaction medium and the structure of the enones can all influence the regioselectivity of the nucleophilic alkylation reactions, the hard/soft nature of the carbanions played a major role. By using the 1,4- and 1,2-addition product ratio as a probe to determine the hard/soft nature of the above-mentioned four halogenated carbanions, the order of the softness of these carbanions can be given as follows: [(PhSO2)(2)CF-] (20) approximate to PhSO2CO2- (32) > PhSO2CHF- (31) > PhSO2CF2- (30). In the case of fluoroalkylation of aryne (35 as the precursor) and alpha,beta-acetylenic ketones 46 with fluorobis(phenyl sulforyl) methane (21), fluorobis(phenylsulfonyl)methylated arenes 36 and beta-fluorobis(phenylsulfonyl)methylated alpha,beta-enones 47 were obtained as the corresponding products in good yields. During the reaction between 2-fluoro-2-(phenylsulfonyl)acetophenone (34) and arynes or activated alkynes 46, an intramolecular tandem reaction process leads to the formation of acyl-fluoroalkylated arenes 43 or alpha-acyl-beta-fluoroalkylated alpha-beta-enones 48. It turned out that the softness of a fluorine-bearing carbanion (such as 20 or 33 derived from 21 or 34) plays a crucial role for the success of the nucleophilic fluoroalkylation reactions with arynes and some activated alkynes (alpha,beta-acetylenic ketones).
语种: 英语
相关网址: 查看原文
WOS记录号: WOS:000257953600005
Citation statistics:
内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/24035
Appears in Collections:中科院有机氟化学重点实验室_期刊论文

Files in This Item: Download All
File Name/ File Size Content Type Version Access License
2008171.pdf(648KB)----开放获取--View Download

Recommended Citation:
Ni CF,Zhang LJ,Hu JB. Nucleophilic fluoroalkylation of alpha,beta-enones, arynes, and activated alkynes with fluorinated sulfones: Probing the hard/soft nature of fluorinated carbanions[J]. J. Org. Chem.,2008,73(15):5699-5713.
Service
Recommend this item
Sava as my favorate item
Show this item's statistics
Export Endnote File
Google Scholar
Similar articles in Google Scholar
[倪传法]'s Articles
[张来俊]'s Articles
[胡金波]'s Articles
CSDL cross search
Similar articles in CSDL Cross Search
[倪传法]‘s Articles
[张来俊]‘s Articles
[胡金波]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
Add to CiteULike Add to Connotea Add to Del.icio.us Add to Digg Add to Reddit
文件名: 2008171.pdf
格式: Adobe PDF
此文件暂不支持浏览
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace