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DOI | 10.1126/science.aat5440 |
Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations | |
Popov, Stasik1; Shao, Brian1; Bagdasarian, Alex L.1; Benton, Tyler R.1; Zou, Luyi1,2; Yang, Zhongyue1,3; Houk, K. N.1; Nelson, Hosea M.1 | |
2018-07-27 | |
发表期刊 | SCIENCE |
ISSN | 0036-8075 |
EISSN | 1095-9203 |
出版年 | 2018 |
卷号 | 361期号:6400页码:381-+ |
文章类型 | Article |
语种 | 英语 |
国家 | USA; Peoples R China |
英文摘要 | Vinyl carbocations have been the subject of extensive experimental and theoretical studies over the past five decades. Despite this long history in chemistry, the utility of vinyl cations in chemical synthesis has been limited, with most reactivity studies focusing on solvolysis reactions or intramolecular processes. Here we report synthetic and mechanistic studies of vinyl cations generated through silylium-weakly coordinating anion catalysis. We find that these reactive intermediates undergo mild intermolecular carbon-carbon bond-forming reactions, including carbon-hydrogen (C-H) insertion into unactivated sp(3) C-H bonds and reductive Friedel-Crafts reactions with arenes. Moreover, we conducted computational studies of these alkane C-H functionalization reactions and discovered that they proceed through nonclassical, ambimodal transition structures. This reaction manifold provides a framework for the catalytic functionalization of hydrocarbons using simple ketone derivatives. |
领域 | 地球科学 ; 气候变化 ; 资源环境 |
收录类别 | SCI-E |
WOS记录号 | WOS:000439923700039 |
WOS关键词 | MOLECULAR-ORBITAL THEORY ; ELECTRONIC-STRUCTURE ; ORGANIC-COMPOUNDS ; GAS-PHASE ; SOLVOLYSIS ; CHEMISTRY ; REARRANGEMENT ; GENERATION ; ENERGIES ; ALKYNES |
WOS类目 | Multidisciplinary Sciences |
WOS研究方向 | Science & Technology - Other Topics |
引用统计 | |
文献类型 | 期刊论文 |
条目标识符 | http://119.78.100.173/C666/handle/2XK7JSWQ/199241 |
专题 | 地球科学 资源环境科学 气候变化 |
作者单位 | 1.Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA; 2.Jilin Univ, Inst Theoret Chem, Lab Theoret & Computat Chem, Changchun 130023, Jilin, Peoples R China; 3.MIT, Dept Chem Engn, Cambridge, MA 02139 USA |
推荐引用方式 GB/T 7714 | Popov, Stasik,Shao, Brian,Bagdasarian, Alex L.,et al. Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations[J]. SCIENCE,2018,361(6400):381-+. |
APA | Popov, Stasik.,Shao, Brian.,Bagdasarian, Alex L..,Benton, Tyler R..,Zou, Luyi.,...&Nelson, Hosea M..(2018).Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations.SCIENCE,361(6400),381-+. |
MLA | Popov, Stasik,et al."Teaching an old carbocation new tricks: Intermolecular C-H insertion reactions of vinyl cations".SCIENCE 361.6400(2018):381-+. |
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