Mechanistic insight of TiCl4 catalyzed formal [3+3] cyclization of 1,3-bis(silyl enol ethers) with 1,3-dielectrophiles

被引：7
|
作者：
Nisa, Riffat Un [1 ]
Maria [1 ]
Wasim, Fatima [1 ]
Mahmood, Tariq [1 ]
Ludwig, Ralf [2 ,3 ]
Ayub, Khurshid [1 ]
机构：
[1] COMSATS Inst Informat Technol, Dept Chem, Abbottabad, Pakistan
[2] Univ Rostock, Leibniz Inst Katalyse eV, D-18059 Rostock, Germany
[3] Univ Rostock, Dept Phys Chem, D-18059 Rostock, Germany
来源：
RSC Advances | 2015年 / 5卷 / 114期
关键词：
TITANIUM TETRACHLORIDE; COMPLEXES; ANNULATION; PHENOLS; SELECTIVITY;
D O I：
10.1039/c5ra19238b
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
The mechanism of TiCl4 mediated formal [3 + 3] cyclization of 1,3-bis(silyl enol ethers) with 1,3-dielectrophiles is studied at the B3LYP level of density functional theory (DFT) to rationalize the experimental regioselectivity. Methyl and trifluoromethyl substituted 1,3 dielectrophiles are studied theoretically since they show different regioselectivities. Two different mechanisms involving 1,2 and 1,4 addition of 1,3-bis(silyl enol ethers) on 1,3-dielectrophiles are studied for each dienophile. The intramolecular transition metal catalyzed and non-catalyzed dynamic shift of the silyl moiety is also studied. The structure of the 1,3 dienophile and the associated Mulliken charges are the driving forces for different regioselectivities in methyl and trifluoromethyl dienophiles.
引用
收藏
页码：94304 / 94314
页数：11
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