Intermolecular Radical Addition to Ketoacids Enabled by Boron Activation

doi:10.1021/jacs.9b09099

	Intermolecular Radical Addition to Ketoacids Enabled by Boron Activation
	Xie, Shasha 1; Li, Defang1,2 ; Huang, Hanchu 1; Zhang, Fuyuan1,2 ; Chen, Yiyun1,2
	2019-10-16
发表期刊	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN	0002-7863
EISSN	1520-5126
卷号	141 期号:41 页码:16237-16242
发表状态	已发表
DOI	10.1021/jacs.9b09099
摘要	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.
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收录类别	SCI ; SCIE ; EI ; IC ; CCR
语种	英语
资助项目	Strategic Priority Research Program of the Chinese Academy of Sciences[XDB20020200]
WOS研究方向	Chemistry
WOS类目	Chemistry, Multidisciplinary
WOS记录号	WOS:000491220300010
出版者	AMER CHEMICAL SOC
EI主题词	Chemical activation ; Ketones
WOS关键词	ALPHA-KETO ACIDS ; C-H ALKYLATION ; TITANIUM TRICHLORIDE ; PHENYLBORONIC ACID ; CARBONYL CARBON ; ONE-ELECTRON ; COMPLEXATION ; PHOTOREDOX ; MECHANISM ; ALKYNYLATION
原始文献类型	Article
引用统计
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/80514
专题	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
通讯作者	Chen, Yiyun
作者单位	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
通讯作者单位	物质科学与技术学院
推荐引用方式 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.