A PRACTICAL AND EFFICIENT SYNTHESIS OF ALPHA,BETA-UNSATURATED ACYLSILANES
A PRACTICAL AND EFFICIENT SYNTHESIS OF ALPHA,BETA-UNSATURATED ACYLSILANES
复制标题
DOI：
10.1021/jo00225a083
复制
发表时间：
1985-12-13
影响因子：
3.6
通讯作者：
SZCZEPANSKI, SW
中科院分区：
文献类型：
--
作者：
DANHEISER, RL;FINK, DM;SZCZEPANSKI, SW
4种不同的碳-碳键形成过程，包括有机酸盐共轭加成、2种ticl4介导的共轭烯化、3种Diels-Alder反应、21,3 -偶极环加成、4和我们实验室最近开发的[3+ 2]环化反应。4,5这些反应的合成用途由于产物酰基硅烷可经过各种有用的进一步转化，包括布鲁克反应，2,7氧化为羧酸，8,10和氟化物促进转化为酮类和醛类，而得到加强。虽然以前已经报道了几种合成ß-不饱和酰基硅烷的一般方法，但当应用于合成缺乏ß-取代基的化合物时，如丙烯酰和甲基丙烯酰衍生物7a和7b，这些方法被证明是不令人满意的。毫不奇怪，这些简单但高度
4 variety of carbon-carbon bond forming processes, including organocuprate conjugate additions, 2 TiCl4-mediated con-jugate allylations, 3 Diels-Alder reactions, 21, 3-dipolar cy-cloadditions, 4 and the [3+ 2] annulation reaction recently developed in our laboratory. 4, 5 The synthetic utility of these reactions is enhanced by thefact that the product acylsilanes are subject to a variety of useful further transformations, 6 7including, for example, Brook reactions, 2, 7 oxidation to carboxylic acids, 8 910and fluoride-promoted conversion to ketones and aldehydes. 811, 9 Although several general synthetic approaches to, ß-unsaturated acylsilaneshave previously been report-ed, 2" 4, 8* 1, 10 these methods have proved less than satisfactory when applied to the synthesis of compounds lacking ß-substituents such as the acryloyl and methacryloyl deriv-atives 7a and 7b. Not surprisingly, these simple but highly