Asymmetric Binary-Acid Catalysis in the Inverse-Electron-Demanding Hetero-Diels-Alder Reaction of 3,4-Dihydro-2H-Pyran
文献类型：期刊论文
| 作者 | Lv Jian; Zhong Xingren; Cheng Jin-Pei; Luo Sanzhong |
| 刊名 | ACTA CHIMICA SINICA
 |
| 出版日期 | 2012-07-28 |
| 卷号 | 70期号:14页码:1518-1522 |
| 关键词 | Asymmetric Catalysis Hetero-diels-alder Reaction Indium Bromide Chiral Calcium Phosphate 3 4-dihydro-2h-pyran |
| ISSN号 | 0567-7351 |
| DOI | 10.6023/A12060346 |
| 英文摘要 | Chiral dihydropyrans are important structural units in a plethora of bio-active natural products. Inverse-electrondemanding hetero-Diels-Alder reaction between alpha,beta-unsaturated enones/enals and olefins represents one of the most straightforward pathway to access chiral dihyropyrans moieties. Though this reaction has been much explored in asymmetric catalysis, new catalytic strategy or catalysts are still desirable in order to further address the limited scopes and applicability. Previously, we have developed asymmetric binary acid catalysis (ABC) as a powerful combinatorial approach for chiral strong acid catalysis. In principle, the ABC strategy utilizes chiral Bronsted acid, e.g. chiral phosphoric diester acid, as dual ligand and acid, in concert with typical metal Lewis acid, resulting in synergistic catalysis due to their mutually enhanced acidity/electrophilicity as well as the endowed multi-activation sites. To advance the application of ABC strategy in the above mentioned reaction, we have found that the use of metal salt of chiral phosphoric acid instead of free phosphoric acid in the presence of an achiral Lewis acid, led to much improved activity and stereoselectivity, thus providing a conceptual advance to include two Lewis acids combinations in ABC catalysis. The obtained optimal Lewis acids combination, InBr3 and Ca(1c)(2), was found to be an effective and selective catalyst for the HDA reaction of 3,4-dihydro-2H-pyrans. In the presence of InBr3 (2.5 mol%) and Ca(1c) (2.5 mol%), the reaction occurred smoothly to afford the desired 3,4-dihydro-2H-pyrans in high yield (85%-98%), with moderate to excellent diastereoselectivity (70 : 30-99 : 1, endolexo) and enantioselectivity (up to 94% ee) under 25 degrees C in CH2Cl2. Different enol ethers 2 and beta,gamma-unsaturated alpha-ketoesters 3 all worked well with excellent diastereoselectivity (94 : 6) and good enantioselectivity under the optimal reaction conditions. |
| 语种 | 英语 |
| WOS记录号 | WOS:000308051800002 |
| 出版者 | SCIENCE PRESS |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/49303]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Lv Jian |
| 作者单位 | Chinese Acad Sci, Inst Chem, CAS Key Lab Mol Recognit & Funct, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Lv Jian,Zhong Xingren,Cheng Jin-Pei,et al. Asymmetric Binary-Acid Catalysis in the Inverse-Electron-Demanding Hetero-Diels-Alder Reaction of 3,4-Dihydro-2H-Pyran[J]. ACTA CHIMICA SINICA,2012,70(14):1518-1522. |
| APA | Lv Jian,Zhong Xingren,Cheng Jin-Pei,&Luo Sanzhong.(2012).Asymmetric Binary-Acid Catalysis in the Inverse-Electron-Demanding Hetero-Diels-Alder Reaction of 3,4-Dihydro-2H-Pyran.ACTA CHIMICA SINICA,70(14),1518-1522. |
| MLA | Lv Jian,et al."Asymmetric Binary-Acid Catalysis in the Inverse-Electron-Demanding Hetero-Diels-Alder Reaction of 3,4-Dihydro-2H-Pyran".ACTA CHIMICA SINICA 70.14(2012):1518-1522. |
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来源：化学研究所
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