Reactions of an Intramolecular Frustrated Lewis Pair with Unsaturated Substrates: Evidence for a Concerted Olefin Addition Reaction

被引：193

作者：

Moemming, Cornelia M. ^{[1
]}

Froemel, Silke ^{[1
]}

Kehr, Gerald ^{[1
]}

Froehlich, Roland ^{[1
]}

Grimme, Stefan ^{[1
]}

Erker, Gerhard ^{[1
]}

机构：

[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 34期

关键词：

HETEROLYTIC DIHYDROGEN ACTIVATION; FREE CATALYTIC-HYDROGENATION; NONLINEAR-OPTICAL PROPERTIES; ZETA-VALENCE QUALITY; GAUSSIAN-BASIS SETS; METAL-FREE; MOLECULAR-STRUCTURES; COOPERATIVE CATALYSIS; 3-COMPONENT REACTIONS; RHODIUM(I) COMPLEXES;

D O I：

10.1021/ja903511s

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The intramolecular frustrated Lewis pair (mesityl)(2)P-CH2-CH2-B(C6F5)(2) was generated in situ by HB(C6F5)(2) hydroboration of dimesitylvinylphosphine. The compound reacts with 1-pentyne by C-H bond cleavage. It undergoes a 1,2-addition to the carbonyl group of trans-cinnamic aldehyde to yield a zwitterionic six-membered heterocycle by B-O and P-C bond formation. The Lewis pair regioselectively adds to the electron-rich C=C double bond of ethyl vinyl ether, and it selectively undergoes an exo-cis-2,3-addition to norbornene. A combined experimental/theoretical study suggests that this reaction takes place in an asynchronous concerted fashion with the B-C bond being formed in slight preference to the P-C bond. The addition products were characterized by X-ray crystal structure analyses.

引用

页码：12280 / 12289

页数：10

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