Development of a Continuous-Flow System for Asymmetric Hydrogenation Using Self-Supported Chiral Catalysts

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	Development of a Continuous-Flow System for Asymmetric Hydrogenation Using Self-Supported Chiral Catalysts
	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)
刊名	Chem.-Eur. J.
	2009
卷号	15 期号:38 页码:9855-9867
ISSN号	0947-6539
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
通讯作者	丁奎岭
英文摘要	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.
学科主题	金属有机化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1002/chem.200900899
语种	英语
WOS记录号	WOS:000270435600029
公开日期	2013-02-22
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/17853]
专题	上海有机化学研究所_金属有机化学国家重点实验室
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.