| Chiral Ligands derived from Abrine 8. An experimental and theoretical study of free ligand conformational preferences and the addition of diethylzinc to benzaldehyde | |
| Zhu, HJ; Jiang, JX; Saebo, S; Pittman, CU | |
| 2005-01-07 | |
| 发表期刊 | JOURNAL OF ORGANIC CHEMISTRY
 |
| ISSN | 0022-3263 |
| 卷号 | 70期号:1页码:261-267 |
| 摘要 | Three structurally similar series of 1,2,3,4-tetrahydro-beta-carboline ligands, 4a-d, 6a-d and 7ad-d, and two series of chiral oxazolidines, 8a-d and 9a-g, were synthesized and used as chiral catalysts in the addition of diethylzinc to benzaldehyde. The enantio selectivities of the resulting 1-phenyl-1-propanol were obtained in each case, and these ee values were, in most cases, related to the conformational populations of the free ligand as expressed by the calculated differences in the energies of the ligand conformations formed by inversion at nitrogen. This suggested the possible existence of a linear free energy relationship. The effect on enantioselectivity of the carbon chain length of the R group located (1) on the C-3 substituent of 4a-d, 6a-d, and 7a-d or (2) at C-5 in 8a-d and 9a-g was studied in detail. On the basis of the correlations observed and the ligands' structural characterization, a structure was proposed for the transition state during ethyl group transfer when using ligands 8a-d. Furthermore, the change in enantioselectivity was successfully predicted when diastereomeric ligands 11 and 12 were compared in this chiral addition. |
| 关键词 | Catalytic Enantioselective Addition Beta-amino Alcohols Dialkylzinc Reagents Asymmetric Autocatalysis Organometallic Reagents Aromatic-aldehydes Aziridino Alcohols Carbonyl-compounds Ketones Amplification |
| 学科领域 | Chemistry, Organic |
| DOI | 10.1021/jo049754c |
| 收录类别 | SCI ; IC ; CCR |
| 语种 | 英语 |
| WOS记录号 | WOS:000226508600032 |
| 引用统计 | |
| 文献类型 | 期刊论文 |
| 条目标识符 | http://ir.kib.ac.cn/handle/151853/4236 |
| 专题 | 植物化学与西部植物资源持续利用国家重点实验室 |
| 作者单位 | 1.Kunming Inst Bot, Kunming 650204, Yunnan, Peoples R China 2.Mississippi State Univ, Dept Chem, Mississippi State, MS 39762 USA |
| 推荐引用方式 GB/T 7714 | Zhu, HJ,Jiang, JX,Saebo, S,et al. Chiral Ligands derived from Abrine 8. An experimental and theoretical study of free ligand conformational preferences and the addition of diethylzinc to benzaldehyde[J]. JOURNAL OF ORGANIC CHEMISTRY,2005,70(1):261-267. |
| APA | Zhu, HJ,Jiang, JX,Saebo, S,&Pittman, CU.(2005).Chiral Ligands derived from Abrine 8. An experimental and theoretical study of free ligand conformational preferences and the addition of diethylzinc to benzaldehyde.JOURNAL OF ORGANIC CHEMISTRY,70(1),261-267. |
| MLA | Zhu, HJ,et al."Chiral Ligands derived from Abrine 8. An experimental and theoretical study of free ligand conformational preferences and the addition of diethylzinc to benzaldehyde".JOURNAL OF ORGANIC CHEMISTRY 70.1(2005):261-267. |
| 条目包含的文件 | 下载所有文件 | |||||
| 文件名称/大小 | 文献类型 | 版本类型 | 开放类型 | 使用许可 | ||
| 201201060061.pdf（332KB） | 开放获取 | -- | 浏览 下载 | |||
除非特别说明，本系统中所有内容都受版权保护，并保留所有权利。
修改评论