SIOC OpenIR  > 金属有机化学国家重点实验室
Development of a Continuous-Flow System for Asymmetric Hydrogenation Using Self-Supported Chiral Catalysts
其他题名手性自负载催化剂流动相体系在烯烃非均相不对称氢化反应中的应用
Shi L(石磊); Wang XW(王兴旺); Christian A. Sandoval; Wang Z(王正); Li HJ(李洪基); Wu J(吴江); Yu LT(俞立挺); Ding KL(丁奎岭)
2009
发表期刊Chem.-Eur. J.
ISSN0947-6539
卷号15期号:38页码:9855-9867
摘要Well-designed, self-assembled, metal-organic frameworks were constructed by simple mixing of multitopic MonoPhos-based ligands (3; MonoPhos = chiral, monodentate phosphoramidites based on the 1,1'-bi-2-naphthol platform) and [Rh(cod)(2)]BF4 (cod = cycloocta-1,5-diene). This self-supporting strategy allowed for simple and efficient catalyst immobilization without the use of extra added support, giving well-characterized, insoluble (in toluene) polymeric materials (4). The resulting self-supported catalysts (4) showed outstanding catalytic performance for the asymmetric hydrogenation of a number of alpha-dehydroamino acids (5) and 2-aryl enamides (7) with enantiomeric excess (ee) ranges of 94-98% and 90-98%, respectively. The linker moiety in 4 influenced the reactivity significantly, albeit with slight impact on the enantioselectivity. Acquisition of reaction profiles under steady-state conditions showed 4h and 4i to have the highest reactivity (turnover frequency (TOF) = 95 and 97 h(-1) at 2 atm, respectively), whereas appropriate substrate/catalyst matching was needed for optimum chiral induction. The former was recycled 10 times without loss in ee (95-96%), although a drop in TOF of approximately 20% per cycle was observed. The estimation of effective catalytic sites in self-supported catalyst 4e was also carried out by isolation and hydrogenation of catalyst-substrate complex, showing about 37% of the Rh-1 centers in the self-supported catalyst 4e are accessible to substrate 5c in the catalysis. A continuous flow reaction system using an activated C/4h mixture as stationary-phase catalyst for the asymmetric hydrogenation of 5b was developed and run continuously for a total of 144 h with >99% conversion and 96-97% enantioselectivity. The total Rh leaching in the product solution is 1.7% of that in original catalyst 4h.
学科领域金属有机化学
部门归属上海有机所
URL查看原文
收录类别SCI
语种英语
WOS记录号WOS:000270435600029
引用统计
被引频次:38[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/17853
专题金属有机化学国家重点实验室
通讯作者Ding KL(丁奎岭)
推荐引用方式
GB/T 7714
Shi L,Wang XW,Christian A. Sandoval,et al. Development of a Continuous-Flow System for Asymmetric Hydrogenation Using Self-Supported Chiral Catalysts[J]. Chem.-Eur. J.,2009,15(38):9855-9867.
APA 石磊.,王兴旺.,Christian A. Sandoval.,王正.,李洪基.,...&丁奎岭.(2009).Development of a Continuous-Flow System for Asymmetric Hydrogenation Using Self-Supported Chiral Catalysts.Chem.-Eur. J.,15(38),9855-9867.
MLA 石磊,et al."Development of a Continuous-Flow System for Asymmetric Hydrogenation Using Self-Supported Chiral Catalysts".Chem.-Eur. J. 15.38(2009):9855-9867.
条目包含的文件
文件名称/大小 文献类型 版本类型 开放类型 使用许可
2009091.pdf(528KB) 开放获取--请求全文
个性服务
推荐该条目
保存到收藏夹
查看访问统计
导出为Endnote文件
谷歌学术
谷歌学术中相似的文章
[石磊]的文章
[王兴旺]的文章
[Christian A. Sandoval]的文章
百度学术
百度学术中相似的文章
[石磊]的文章
[王兴旺]的文章
[Christian A. Sandoval]的文章
必应学术
必应学术中相似的文章
[石磊]的文章
[王兴旺]的文章
[Christian A. Sandoval]的文章
相关权益政策
暂无数据
收藏/分享
所有评论 (0)
暂无评论
 

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。