Solvent-dependent regioselectivity of hydrogen chloride-mediated ring opening of alkylidenecyclopropanone acetal

被引：4

作者：

Fujita, Morifumi ^{[1
]}

Hanagiri, Shinji ^{[1
]}

Okuyama, Tadashi ^{[1
]}

机构：

[1] Univ Hyogo, Himeji Inst Technol, Grad Sch Mat Sci, Kamigori, Hyogo 6781297, Japan

来源：

TETRAHEDRON LETTERS | 2006年 / 47卷 / 25期

关键词：

cyclopropane; bronsted acid; regioselectivity; ring opening;

D O I：

10.1016/j.tetlet.2006.04.067

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Ring opening reactions of 2-cyclohexylidene-3,3-dimethylcyclopropanone acetal (1) are readily induced by treatment of hydrogen chloride in various solvents. Bond cleavage takes place at the C1-C2 or C2-C3 bond, and the ratio of C1-C2/C2-C3 cleavages changes from > 99/1 to < 1/99 depending on the solvent. The two modes of bond cleavage must be initiated by protonations at the carbon-carbon double bond and the acetal oxygen, respectively. The regioselectivity can be rationalized by the rate-determining protonation at carbon and the equilibrium protonation at oxygen. (c) 2006 Elsevier Ltd. All rights reserved.

引用

页码：4145 / 4148

页数：4

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