Probing for a Leaving Group Effect on the Generation and Reactivity of Phenyl Cations

被引：19

作者：

Abitelli, Erika ^{[1
]}

Protti, Stefano ^{[1
]}

Fagnoni, Maurizio ^{[1
]}

Albini, Angelo ^{[1
]}

机构：

[1] Univ Pavia, PhotoGreenLab, Dept Chem, I-27100 Pavia, Italy

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2012年 / 77卷 / 07期

关键词：

CROSS-COUPLING REACTIONS; ARYL MESYLATES; HECK REACTION; PHOTOCHEMISTRY; EFFICIENT; PHOTODEHALOGENATION; PROTODESILYLATION; PHOTOHETEROLYSIS; NUCLEOPHILICITY; PHOSPHATES;

D O I：

10.1021/jo300290v

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Phenyl cations are smoothly generated by the photoheterolytic cleavage of an Ar-LG bond (LG = leaving group). With the aim of evaluating the scope of the method, a series of 4-methoxy-2-(trimethylsilyl)phenyl derivatives (sulfonic, LG = MeSO3 and CF3SO3, phosphate, LG = (EtO)(2)(O)PO esters and the corresponding chloride) have been compared as probes for evaluating the leaving group ability. The photocleavage was a general reaction, with the somewhat surprising order (EtO)(2)(O)PO similar to Cl > CF3SO3 > MeSO3 (Phi = 0.50 to 0.16 in CF3CH2OH and lower values in MeCN-H2O). The ensuing reactions did not depend on the LGs but only on the structure of the phenyl cation (the silyl group tuned the triplet to singlet intersystem crossing and the electrophilicity) and on the medium (formation of a complex with water slowed the electrophilic reactions).

引用

页码：3501 / 3507

页数：7

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