Chiral Bidentate Boryl Ligand Enabled Iridium-Catalyzed Asymmetric C(sp(2))-H Borylation of Diarylmethylamines
文献类型：期刊论文
| 作者 | Zou, Xiaoliang1; Zhao, Haonan1; Li, Yinwu2; Gao, Qian1; Ke, Zhuofeng2; Xu, Senmiao1,3 |
| 刊名 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
 |
| 出版日期 | 2019-04-03 |
| 卷号 | 141期号:13页码:5334-5342 |
| ISSN号 | 0002-7863 |
| DOI | 10.1021/jacs.8b13756 |
| 通讯作者 | Ke, Zhuofeng(kezhf3@mail.sysu.edu.cn) ; Xu, Senmiao(senmiaoxu@licp.cas.cn) |
| 英文摘要 | Optically active organoboronic acids and their derivatives are an important family of target compounds in organic chemistry, catalysis, and medicinal chemistry. Yet there are rare asymmetric catalytic examples reported for the synthesis of these compounds via atom and step economic ways. Herein, we report a chelate-directed iridium-catalyzed asymmetric C(sp(2))-H borylation of aromatic C-H bonds directed by free amine groups. The success of these transformations relies on a novel family of chiral bidentate boryl ligands (L). They can be synthesized straightforwardly in three steps starting from readily available (S,S)-1,2- diphenyl-1,2-ethanediamie ((S,S)-DPEN). The Ir-catalyzed C(sp(2))-H borylation comprises two parts. The first part is desymmetrization of prochiral diarylmethylamines. In the presence of L3/Ir, a vast array of corresponding borylated products were obtained with high regioselectivity and good to excellent enantioselectivities (26 examples, up to 96% ee). The second part, kinetic resolution of racemic diarylmethylamines, was also conducted. Good selectivity values (up to 68%, 11 examples) were obtained when L8 was used. We also demonstrated the synthetic utility of the current method on gram-scale reaction for several transformations. The C-B bonds of borylated products could be converted to a variety of functionalities including C-O, C-C, C-C, C-Br, and C-P bonds. Finally, we performed DFT calculations of desymmetrization to understand its reaction pathways. |
| 收录类别 | SCI |
| WOS关键词 | C-H BORYLATION ; DIRECTED ORTHO BORYLATION ; ENANTIOSELECTIVE SYNTHESIS ; REGIOSELECTIVE BORYLATION ; C(SP(3))-H BORYLATION ; BOND ACTIVATION ; DIELS-ALDER ; ARENES ; SILYLATION ; EFFICIENT |
| WOS研究方向 | Chemistry |
| WOS类目 | Chemistry, Multidisciplinary |
| 语种 | 英语 |
| 出版者 | AMER CHEMICAL SOC |
| WOS记录号 | WOS:000463843700038 |
| URI标识 | http://www.irgrid.ac.cn/handle/1471x/2555507 |
| 专题 | 寒区旱区环境与工程研究所 |
| 通讯作者 | Ke, Zhuofeng; Xu, Senmiao |
| 作者单位 | 1.Univ Chinese Acad Sci, Chinese Acad Sci, Lanzhou Inst Chem Phys,Suzhou Res Inst, Ctr Excellence Mol Synth,State Key Lab Oxo Synth, Lanzhou 73000, Gansu, Peoples R China 2.Sun Yat Sen Univ, Sch Mat Sci & Engn, PCFM Lab, Guangzhou 510275, Guangdong, Peoples R China 3.Hangzhou Normal Univ, Minist Educ, Key Lab Organosilicon Chem & Mat Technol, Hangzhou 311121, Zhejiang, Peoples R China |
| 推荐引用方式 GB/T 7714 | Zou, Xiaoliang,Zhao, Haonan,Li, Yinwu,et al. Chiral Bidentate Boryl Ligand Enabled Iridium-Catalyzed Asymmetric C(sp(2))-H Borylation of Diarylmethylamines[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2019,141(13):5334-5342. |
| APA | Zou, Xiaoliang,Zhao, Haonan,Li, Yinwu,Gao, Qian,Ke, Zhuofeng,&Xu, Senmiao.(2019).Chiral Bidentate Boryl Ligand Enabled Iridium-Catalyzed Asymmetric C(sp(2))-H Borylation of Diarylmethylamines.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,141(13),5334-5342. |
| MLA | Zou, Xiaoliang,et al."Chiral Bidentate Boryl Ligand Enabled Iridium-Catalyzed Asymmetric C(sp(2))-H Borylation of Diarylmethylamines".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 141.13(2019):5334-5342. |
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来源：寒区旱区环境与工程研究所
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