PdII-catalyzed domino heterocyclization/cross-coupling of α-allenols and α-allenic esters:: Efficient preparation of functionalized buta-1,3-dienyl dihydrofurans

被引：26

作者：

Alcaide, Benito ^{[1
]}

Almendros, Pedro ^{[2
]}

del Campo, Teresa Martinez ^{[1
]}

Carrascosa, Rocio ^{[1
]}

机构：

[1] Univ Complutense Madrid, Dept Quim Organ 1, Fac Quim, E-28040 Madrid, Spain

[2] CSIC, Consejo Super Invest Cientif, Inst Quim Organ Gen, E-28006 Madrid, Spain

来源：

CHEMISTRY-AN ASIAN JOURNAL | 2008年 / 3卷 / 07期

关键词：

allenes; cyclization; heterocycles; palladium; regioselectivity;

D O I：

10.1002/asia.200800031

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A mild, palladium(II)-catalyzed reaction of alpha-allenols with alpha-allenic esters in a heterocyclization/cross-coupling sequence, applicable to a wide range of substitution patterns, has been developed for the preparation of 2,3,4,trifunctionalized 2,5-dihydrofurans. Our studies indicate high levels of chemo- and regiocontrol. The possibility of using optically active substrates as well as substrates of increased steric demand, such as tertiary alpha-allenols, makes this novel sequence of heterocyclization/cross-coupling an attractive method in organic synthesis. The cur-rent mechanistic hypothesis invokes a regiocontrolled palladium(II)-mediated intramolecular oxypalladation of the free allenol component, that then undergoes a cross-coupling reaction with the allenic ester partner, followed by a trans-beta-deacyloxypalladation with concomitant regeneration of the Pd-II species.

引用

页码：1140 / 1145

页数：6

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