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| Intermolecular Radical Addition to Ketoacids Enabled by Boron Activation | |
| 2019-10-16 | |
| Source Publication | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
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| ISSN | 0002-7863 |
| EISSN | 1520-5126 |
| Volume | 141Issue:41Pages:16237-16242 |
| Status | 已发表 |
| DOI | 10.1021/jacs.9b09099 |
| Abstract | The intermolecular radical addition to the carbonyl group is difficult due to the facile fragmentation of the resulting alkoxyl radical. To date, the intermolecular radical addition to ketones, a valuable approach to construct quaternary carbon centers, remains a formidable synthetic challenge. Here, we report the first visible-light-induced intermolecular alkyl boronic acid addition to aketoacids enabled by the Lewis acid activation. The in situ boron complex formation is confirmed by various spectroscopic measurements and mechanistic probing experiments, which facilitates various alkyl boronic acid addition to the carbonyl group and prevents the cleavage of the newly formed C-C bond. Diversely substituted lactates can be synthesized from readily available alkyl boronic acids and ketoacids at room temperature merely under visible light irradiation, without any additional reagent. This boron activation approach can be extended to alkyl dihydropyridines as radical precursors with external boron reagents for primary, secondary, and tertiary alkyl radical additions. The pharmaceutically useful anticholinergic precursors are easily scaled up in multigrams under metal-free conditions in flow reactors. |
| URL | 查看原文 |
| Indexed By | SCI ; SCIE ; EI ; IC ; CCR |
| Language | 英语 |
| Funding Project | Strategic Priority Research Program of the Chinese Academy of Sciences[XDB20020200] |
| WOS Research Area | Chemistry |
| WOS Subject | Chemistry, Multidisciplinary |
| WOS ID | WOS:000491220300010 |
| Publisher | AMER CHEMICAL SOC |
| EI Keywords | Chemical activation ; Ketones |
| WOS Keyword | ALPHA-KETO ACIDS ; C-H ALKYLATION ; TITANIUM TRICHLORIDE ; PHENYLBORONIC ACID ; CARBONYL CARBON ; ONE-ELECTRON ; COMPLEXATION ; PHOTOREDOX ; MECHANISM ; ALKYNYLATION |
| Original Document Type | Article |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/80514 |
| Collection | 物质科学与技术学院_博士生 物质科学与技术学院_特聘教授组_陈以昀组 物质科学与技术学院_硕士生 |
| Corresponding Author | Chen, Yiyun |
| Affiliation | 1.Univ Chinese Acad Sci, Chinese Acad Sci, State Key Lab Bioorgan & Nat Prod Chem, Ctr Excellence Mol Synth,Shanghai Inst Organ Chem, 345 Lingling Rd, Shanghai 200032, Peoples R China 2.ShanghaiTech Univ, Sch Phys Sci & Technol, 100 Haike Rd, Shanghai 201210, Peoples R China |
| Corresponding Author Affilication | School of Physical Science and Technology |
| Recommended Citation GB/T 7714 | Xie, Shasha,Li, Defang,Huang, Hanchu,et al. Intermolecular Radical Addition to Ketoacids Enabled by Boron Activation[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2019,141(41):16237-16242. |
| APA | Xie, Shasha,Li, Defang,Huang, Hanchu,Zhang, Fuyuan,&Chen, Yiyun.(2019).Intermolecular Radical Addition to Ketoacids Enabled by Boron Activation.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,141(41),16237-16242. |
| MLA | Xie, Shasha,et al."Intermolecular Radical Addition to Ketoacids Enabled by Boron Activation".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 141.41(2019):16237-16242. |
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