STRUCTURE AND ASYMMETRIC DIELS-ALDER REACTIONS OF OPTICALLY ACTIVE ALLENE-1,3-DICARBOXYLATES
STRUCTURE AND ASYMMETRIC DIELS-ALDER REACTIONS OF OPTICALLY ACTIVE ALLENE-1,3-DICARBOXYLATES
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光学活性联烯-1,3-二羧酸酯的结构和不对称狄尔斯-阿尔德反应
DOI：
10.1021/jo951762t
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发表时间：
1996
影响因子：
3.6
通讯作者：
K. Kanematsu
中科院分区：
文献类型：
--
作者：
I. Ikeda;K. Honda;E. Ōsawa;M. Shiro;M. Aso;K. Kanematsu
制备了光学活性的丙二烯-1，3-二羧酸酯（1a和2a），它们含有轴向不对称的丙二烯部分。1a和2a与环戊二烯的Diels−桤木反应，由于联烯部分的轴向不对称性和有效的次级轨道相互作用，通过二烯和亲二烯体的空间有利途径的结合，得到1：1（1a或2a与环戊二烯）的内加合物3a和4a。3a和4a的绝对构型由化学转化和X射线衍射确定。通过X射线分析，1a的轴向不对称的绝对构型也被确定为R。
Optically active allene-1,3-dicarboxylates (1a and 2a), which contain the axial asymmetry of the allene moiety, were prepared. The Diels−Alder reaction of 1a and 2a with cyclopentadiene afforded the 1:1 (1a or 2a to cyclopentadiene) endo adducts 3a and 4a through the combination of the sterically favorable approach of the diene and the dienophile owing to the axial asymmetry of the allene moiety and the effective secondary orbital interaction. The absolute configurations of 3a and 4a were determined by chemical transformation and X-ray analysis. The absolute configuration of the axial asymmetry of 1a was also determined to be R by X-ray analysis.