Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand

doi:10.6023/A17040144

	Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand
	Zhang, YL; Wang, M; Cao, P; Liao, J; Liao, J (reprint author), Chinese Acad Sci, Chengdu Inst Biol, Nat Prod Res Ctr, Chengdu 610041, Sichuan, Peoples R China.; Liao, J (reprint author), Univ Chinese Acad Sci, Beijing 100049, Peoples R China.
刊名	ACTA CHIMICA SINICA
	2017
卷号	75 期号:8 页码:794-797
关键词	Cu-catalyzed Chiral Sulfoxide Phosphine Styrenes Enantioselective Aminoboration Beta-hydroxylalkylamines
DOI	10.6023/A17040144
产权排序	1
文献子类	Article
英文摘要	To date, copper catalysis has become an attractive approach to access multifunctional alkylborons through borylative coupling processes, many important protocols such as carboboration, stannylboration and aminoboration were developed. Among these methods, however, there is no report involving enantioselective aminoboration of simple styrene substrates, which can generate a class of useful chiral compounds. In this work, an enantioselective Cu-catalyzed aminoboration of styrenes by using a chiral sulfoxide-phosphine (SOP) ligand was developed, chiral beta-aminoalkylboranes were obtained in satisfied yields and ee values, and these products can be readily converted to a class of valuable beta-hydroxylalkylamines. A general procedure for the aminoboration of styrenes is as following: in glove box, CuCl (0.02 mmol), chiral sulfoxide phosphine L1 (0.022 mmol) and 2.0 mL of dried tetrahydrofuran were added into a flame-dried tube, the resolved solution was stirred for 30 min at room temperature, then bis(pinacolato) diboron (B(2)pin(2)) (0.3 mmol), t-BuOLi (0.6 mmol) and styrene (0.2 mmol) were added. The tube was taken out of the glove box and cooled to 0 degrees C. Electrophilic amination reagent, O-benzoyl-N,Ndibenzylhydroxylamine (2a, 0.3 mmol), was dissolved in 1.0 mL of ethyl acetate and added to the mixture, the resolved mixture was stirred at 0 degrees C for 24 h. The crude product was filtered through a celite pad, concentrated and oxidized by NaBO3 center dot 4H(2)O. The mixture was extracted three times with ethyl acetate, concentrated and purified with silica gel chromatography to give the desired beta-hydroxylalkylamines, the enantioselective excess of products were determined by chiral HPLC analysis. Broad substrate scope which related to steric and electronic effect were compatible in this catalysis under the standard conditions. To demonstrate the utility of this method, a gram scale experiment was performed and the desired product was obtained in 92% isolated yield and 90% ee. The benzyl group of products can be readily removed via a Pd/C-catalyzed hydrogenation process and the corresponding product with a free amino group in excellent yield (95%).
学科主题	Chemistry
语种	英语
资助机构	Project supported by the National Natural Science Foundation of China (Nos. 21472184, 21572218 and 21402186). ; National Natural Science Foundation of China [21472184, 21572218, 21402186] ; Project supported by the National Natural Science Foundation of China (Nos. 21472184, 21572218 and 21402186). ; National Natural Science Foundation of China [21472184, 21572218, 21402186] ; Project supported by the National Natural Science Foundation of China (Nos. 21472184, 21572218 and 21402186). ; National Natural Science Foundation of China [21472184, 21572218, 21402186] ; Project supported by the National Natural Science Foundation of China (Nos. 21472184, 21572218 and 21402186). ; National Natural Science Foundation of China [21472184, 21572218, 21402186]
内容类型	期刊论文
源URL	[http://210.75.237.14/handle/351003/29217]
专题	成都生物研究所_天然产物研究
通讯作者	Liao, J (reprint author), Chinese Acad Sci, Chengdu Inst Biol, Nat Prod Res Ctr, Chengdu 610041, Sichuan, Peoples R China.; Liao, J (reprint author), Univ Chinese Acad Sci, Beijing 100049, Peoples R China.
推荐引用方式 GB/T 7714	Zhang, YL,Wang, M,Cao, P,et al. Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand[J]. ACTA CHIMICA SINICA,2017,75(8):794-797.
APA	Zhang, YL,Wang, M,Cao, P,Liao, J,Liao, J ,&Liao, J .(2017).Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand.ACTA CHIMICA SINICA,75(8),794-797.
MLA	Zhang, YL,et al."Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand".ACTA CHIMICA SINICA 75.8(2017):794-797.