Diastereoselective Diels-Alder reactions of α-fluorinated α,β-unsaturated carbonyl compounds:: Chemical consequences of fluorine substitution.: 2.

被引：69

作者：

Essers, M ^{[1
]}

Mück-Lichtenfeld, C ^{[1
]}

Haufe, G ^{[1
]}

机构：

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

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2002年 / 67卷 / 14期

关键词：

D O I：

10.1021/jo015917a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Two alpha-fluoro alpha,beta-unsaturated carbonyl compounds, i.e., benzyl 2-fluoroacrylate (3) and 2-fluorooct-1-en-3-one (4), as well as the corresponding nonfluorinated parent compounds, were synthesized and subjected to Diels-Alder reactions with cyclopentadiene. The cycloadditions were conducted thermally, microwave-assisted, and Lewis acid-mediated (TiCl4). The fluorinated dienophiles exhibited a lower reactivity and exo diastereoselectivity, while the corresponding nonfluorinated parent compounds reacted endo selectively. DFT calculations suggest that kinetic effects of fluorine determine the stereoselectivity rather than higher thermodynamic stability of the exo products.

引用

页码：4715 / 4721

页数：7

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