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

doi:10.6023/A17040144

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (8): 794-797.DOI: 10.6023/A17040144 Previous Articles Next Articles

Communication

铜催化苯乙烯不对称硼胺化反应

张涌灵^a,b, 王敏^a, 曹鹏^a, 廖建^a,b

a 中国科学院成都生物研究所天然产物研究中心成都 610041;
b 中国科学院大学北京 100049

投稿日期:2017-04-12 发布日期:2017-05-09
通讯作者: 廖建,E-mail:jliao@cib.ac.cn E-mail:jliao@cib.ac.cn
基金资助:
项目受国家自然科学基金（Nos.21472184，21572218和21402186）资助.

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

Zhang Yongling^a,b, Wang Min^a, Cao Peng^a, Liao Jian^a,b

a Natural Products Research Center, Chengdu Institute of Biology, Chinese Academy of Sciences, Chengdu 610041;
b University of Chinese Academy of Sciences, Beijing 100049

Received:2017-04-12 Published:2017-05-09
Contact: 10.6023/A17040144 E-mail:jliao@cib.ac.cn
Supported by:
Project supported by the National Natural Science Foundation of China (Nos.21472184,21572218 and 21402186).

1. Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand.PDF(4547KB)

Abstract

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 β-aminoalkylboranes were obtained in satisfied yields and ee values, and these products can be readily converted to a class of valuable β-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 (B₂pin₂) (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℃. Electrophilic amination reagent, O-benzoyl-N,N-dibenzylhydroxylamine (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℃ for 24 h. The crude product was filtered through a celite pad, concentrated and oxidized by NaBO₃·4H₂O. The mixture was extracted three times with ethyl acetate, concentrated and purified with silica gel chromatography to give the desired β-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%).

Key words: Cu-catalyzed, chiral sulfoxide phosphine, styrenes, enantioselective aminoboration, β-hydroxylalkylamines

Cite this article

Zhang Yongling, Wang Min, Cao Peng, Liao Jian. Copper-Catalyzed Enantioselective Aminoboration of Styrenes with Chiral Sulfoxide Phosphine Ligand[J]. Acta Chim. Sinica, 2017, 75(8): 794-797.

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铜催化苯乙烯不对称硼胺化反应

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

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