Mechanism of the Deprotonation Reaction of Alkyl Benzyl Ethers with n-Butyllithium

被引：7

作者：

Luz Raposo, M. ^{[1
]}

Fernandez-Nieto, Fernando ^{[2
]}

Garcia-Rio, Luis ^{[1
]}

Rodriguez-Dafonte, P. ^{[1
]}

Rita Paleo, M. ^{[2
]}

Javier Sardina, F. ^{[2
]}

机构：

[1] Univ Santiago, Ctr Invest Quim Biol & Mat Mol CIQUS, Dept Quim Fis, Santiago 15782, Spain

[2] Univ Santiago, Ctr Invest Quim Biol & Mat Mol CIQUS, Dept Quim Organ, Santiago 15782, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 29期

关键词：

aggregation; butyllithium; deprotonation; kinetics; mechanism; ARYLLITHIUM REAGENTS-STRUCTURE; OXIDE TETRAFLUOROBORIC ACID; ORGANO-LITHIUM COMPOUNDS; ALPHA-OXY-ORGANOLITHIUM; NMR-SPECTROSCOPY; AGGREGATION BEHAVIOR; NONPERFECT SYNCHRONIZATION; DYNAMIC-BEHAVIOR; INDICATOR SCALE; CARBON ACIDITY;

D O I：

10.1002/chem.201204467

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Kinetic study of the -lithiation of benzyl methyl ether (BME) by nBuLi has revealed that increasing the concentration of the organolithium compound does not necessarily increase the reactivity, and this is a consequence of the reactivities of the different nBuLi aggregates present in solution. We propose a dimer-based mechanism, in which a pre-complexation step is a key process for substrates bearing a donor oxygen atom that can interact with the lithium cation to form mixed dimers. For these studies, we have developed a system based on UV/Vis spectroscopy that allows kinetic measurements to be conducted at -80 degrees C under argon.

引用

页码：9677 / 9685

页数：9

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