Palladium-catalyzed 1,4-acetoxy-trifluoroacetoxylation and 1,4-alkoxy-trifluoroacetoxylation of cyclic 1,3-dienes.: Scope and mechanism

被引：22

作者：

Aranyos, A ^{[1
]}

Szabó, KJ ^{[1
]}

Bäckvall, JE ^{[1
]}

机构：

[1] Uppsala Univ, Dept Organ Chem, S-75121 Uppsala, Sweden

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 08期

关键词：

D O I：

10.1021/jo971738a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Palladium-catalyzed unsymmetrical 1,4-functionalizations of cyclic 1,3-dienes are described. Trifluoroacetate in combination with acetate or alcohols is utilized to obtain 1-acetoxy-4-(trifluoroacetoxy)-2-cycloalkenes and 1-alkoxy-4-(trifluoroacetoxy)-2-cycloalkenes, respectively, with good regio-and stereoselectivities. The chemoselectivity of these reactions relies on the different kinetic stability of the intermediate 4-(trifluoroacetoxy)-, 4-acetoxy-, and 4-methoxy-[eta(3)-(1,2,3)-cycloalkenyl]palladium complexes. Under the acidic reaction conditions employed, the 4-trifluoroacetoxy pi-allyl intermediate is the least stable of the three. Certain mechanistic aspects of the reactions are discussed in the light of DFT calculations.

引用

页码：2523 / 2529

页数：7

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