The Absolute Configuration of Carpaine1
The Absolute Configuration of Carpaine1
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DOI：
10.1021/jo01021a036
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发表时间：
1965-10
影响因子：
3.6
通讯作者：
J. Coke;W. Rice
中科院分区：
文献类型：
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作者：
J. Coke;W. Rice
木瓜生物碱番木瓜碱的绝对构型已确定。 Carpaine 被降解为 (fi)-(—)-3-十四烷醇。 (R)-(-)-3-十四烷醇的绝对构型由(R)-(+)-1,2-环氧丁烷制备得到。 (R)-(+)-1,2-环氧丁烷被还原为(S)-(+)-2-丁醇，其绝对构型是已知的。讨论了相关化合物的立体化学。许多工作人员已经研究了生物碱carpaine (1) 的结构。 Rapoport 和同事 3 以及 Govindachari 和同事 4 5 已经建立了生物碱的总体结构。 Govindachari 和 Narasimhan6 提供了令人信服的证据，证明哌啶环上的甲基和烷基侧链彼此是顺式的。 Tichy和Sicher6利用红外技术表明氨基甲酸甲酯的羟基在哌啶环上是轴向的。所有这些证据都被解释为有利于卡帕因的相对构型，其中所有连接到哌啶环的基团都是顺式的。最近使用质谱技术进行的一项研究7表明，卡帕因由两个相同的取代基组成
The absolute configuration of the papaya alkaloid carpaine has been determined. Carpaine was degraded to (fi)-(—)-3-tetradecanol. The absolute configuration of (R)-(—)-3-tetradecanol was shown by its prepara-tion from (R)-(+)-l, 2-epoxybutane. The (R)-(+)-l, 2-epoxybutane was reduced to (S)-(+)-2-butanol, the absolute configuration of which is known. The stereochemistry of related compounds is discussed.The structure of the alkaloid carpaine (1) has been investigated by a number of workers. Rapoport and co-workers3 and Govindachari andco-workers4 5have established the gross structure of the alkaloid. Govindachari and Narasimhan6 provided convincing proof that the methyl group and the alkyl side chain are cis to each other on the piperidine ring. Tichy and Sicher6 used infrared techniques to show that the hydroxyl group of methyl carpamate is axial on the piperi-dine ring. All this evidence was interpreted in favor of a relative configuration for carpaine in which all the groups attached to the piperidinering are cis. A recent investigation7 using mass spectral techniques has shown that carpaine consists of two identical substituted