| Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper-Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate | |
| Department | OSSO国家重点实验室 |
Ye F(叶飞)1; Zheng ZJ(郑战江)1; Deng WH(邓文慧)1; Zheng LS(郑龙生)1; Deng Y(邓元)1; Xia CG(夏春谷)2 ; Xu LW(徐利文)1,2; Xu LW(徐利文)
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| 2013 | |
| Source Publication | Chemistry - An Asian Journal
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| ISSN | 1861-4728 |
| Volume | 8Issue:9Pages:2242-2253 |
| Abstract | In this work, we have successfully synthesized a new family of chiral Schiff base–phosphine ligands derived from chiral binaphthol (BINOL) and chiral primary amine. The controllable synthesis of a novel hexadentate and tetradentate N,O,P ligand that contains both axial and sp3-central chirality from axial BINOL and sp3-central primary amine led to the establishment of an efficient multifunctional N,O,P ligand for copper-catalyzed conjugate addition of an organozinc reagent. In the asymmetric conjugate reaction of organozinc reagents to enones, the polymer-like bimetallic multinuclear Cu-Zn complex constructed in situ was found to be substrate- selective and a highly excellent catalyst for diethylzinc reagents in terms of enantioselectivity (up to >99% ee). More importantly, the chirality matching between different chiral sources, C2-axial binaphthol and sp3- central chiral phosphine, was crucial to the enantioselective induction in this reaction. The experimental results indicated that our chiral ligand (R,S,S)-L1- and (R,S)-L4-based bimetallic complex catalyst system exhibited the highest catalytic performance to date in terms of enantioselectivity and conversion even in the presence of 0.005 mol% of catalyst (S/C=20 000, turnover number (TON)=17 600). We also studied the tandem silylation or acylation of enantiomerically enriched zinc enolates that formed in situ from copper-L4-complex-catalyzed conjugate addition, which resulted in the high-yield synthesis of chiral silyl enol ethers and enoacetates, respectively. Furthermore, the specialized structure of the present multifunctional N,O,P ligand L1 or L4, and the corresponding mechanistic study of the copper catalyst system were investigated by 31P NMR spectroscopy, circular dichroism (CD), and UV/Vis absorption. |
| Keyword | Asymmetric Catalysis Conjugate Addition Copper n Ligands Zinc |
| Subject Area | 物理化学与绿色催化 |
| DOI | 10.1002/asia.201300544 |
| Funding Organization | the National Natural Science Foundation of China (no. 21173064);the Zhejiang Provincial Natural Science Foundation of China (Q12B020037);the Program for Excellent Young Teachers in Hangzhou Normal University (HNUEYT; JTAS 2011-01-014) |
| Indexed By | SCI |
| If | 3.935 |
| Language | 英语 |
| Funding Project | 均相催化课题组 |
| compositor | 第二作者单位 |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://ir.licp.cn/handle/362003/4864 |
| Collection | 羰基合成与选择氧化国家重点实验室（OSSO） |
| Corresponding Author | Xu LW(徐利文) |
| Affiliation | 1.Hangzhou Normal Univ, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 310012, Zhejiang, Peoples R China 2.Chinese Acad Sci, Lanzhou Inst Chem Phys, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China |
| Recommended Citation GB/T 7714 | Ye F,Zheng ZJ,Deng WH,et al. Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper-Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate[J]. Chemistry - An Asian Journal,2013,8(9):2242-2253. |
| APA | Ye F.,Zheng ZJ.,Deng WH.,Zheng LS.,Deng Y.,...&徐利文.(2013).Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper-Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate.Chemistry - An Asian Journal,8(9),2242-2253. |
| MLA | Ye F,et al."Modulation of Multifunctional N,O,P Ligands for Enantioselective Copper-Catalyzed Conjugate Addition of Diethylzinc and Trapping of the Zinc Enolate".Chemistry - An Asian Journal 8.9(2013):2242-2253. |
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| Chem. Asian J. 2013,（1145KB） | 期刊论文 | 作者接受稿 | 开放获取 | CC BY-NC-SA | View Application Full Text | |
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