Theory-guided design of Bronsted acid-assisted phosphine catalysis: synthesis of dihydropyrones from aldehydes and allenoates

被引:42
作者
Creech, Gardner S. [1 ]
Zhu, Xue-Feng [1 ]
Foncivic, Branden [2 ]
Dudding, Travis [2 ]
Kwon, Ohyun [1 ]
机构
[1] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA
[2] Brock Univ, Dept Chem, St Catharines, ON LS2 3A1, Canada
基金
加拿大创新基金会; 美国国家卫生研究院;
关键词
phosphine; catalysis; Lewis base; Bronsted acid; dihydropyrone; aldehyde; allenoate;
D O I
10.1016/j.tet.2008.04.075
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The phosphine-catalyzed addition of 2,3-butadienoates to aldehydes has been extended to the formation of disubstituted dihydro-2-pyrones. The requisite shift in equilibrium of the intermediate zwitterionic beta-phosphomuin dienolates toward the s-cis intermediate was accomplished through the use of a Bronsted acid additive, which disrupts the favorable Coulombic interaction present in the s-trans intermediate. The detailed nature of the synergistic interactions involving the Bronsted acid additives and phosphine involved in the formation of s-cis beta-phosphonium dienolates was analyzed through a series of DFT calculations. Unlike previously reported annulations of aldehydes with allenoates, where trialkylphosphines are optimal catalysts, in this study triphenylphosphine was also found for the first time to be a suitable catalyst for the synthesis of dihydropyrones. This method provides a one-step route toward functionalized dihydropyrones from simple, stable starting materials. In addition, new reaction pathways of phosphine-catalyzed allene annulations are unveiled, with the formation of dihydropyrones being the first example of dual activation in this sphere. (C) 2008 Elsevier Ltd. All rights reserved.
引用
收藏
页码:6935 / 6942
页数:8
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