Quantum-chemical study on positional selectivity in the trimethylsilylation and sulfonation of pyrrole and N-alkylpyrroles

被引:3
作者
Belen'kii, L. I. [1 ]
Chuvylkin, N. D. [1 ]
Serykh, A. I. [1 ]
Suslov, I. A. [2 ]
机构
[1] Russian Acad Sci, Zelinskii Inst Organ Chem, Moscow 119991, Russia
[2] Russian Acad Sci, Higher Chem Coll, Moscow 119991, Russia
关键词
Experimental Data; Organic Chemistry; Pyrrole; Trimethylsilyl; Electrophilic Substitution;
D O I
10.1007/s11178-005-0343-3
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Positional selectivity (alpha:beta ratio) of electrophilic substitution in pyrrole, N-methylpyrrole, and N-tert-butylpyrrole was analyzed by ab initio [RHF/6-31G(d), MP2/6-31G(d)//RHF/6-31G(d)] and DFT [B3LYP/6-31G(d)] calculations of some sigma-complexes derived from the substrates. The results of calculations with the use as model electrophilic species of trimethylsilyl cation [MP2/6-31G(d)//RHF/6-31G(d) and B3LYP/6-31G(d)] and SO3 molecule [B3LYP/6-31G(d)] instead of proton are fairly consistent with the experimental data, according to which trimethylsilylation of pyrrole and its N-substituted derivatives with trimethylsilyl trifluoromethanesulfonate, as well as sulfonation with pyridine - sulfur trioxide complex, gives the corresponding beta-substituted products.
引用
收藏
页码:1337 / 1340
页数:4
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