2-氮杂降莰烷：蒎烯生物合成中对映异构的莰基碳正离子中间体的氮杂类似物。
2-azapinanes: aza analogues of the enantiomeric pinyl carbocation intermediates in pinene biosynthesis.
机构信息
Department of Chemistry, University of Illinois, Urbana-Champaign, Illinois 61801, USA.
出版信息
Org Lett. 2011 Mar 4;13(5):836-9. doi: 10.1021/ol1027893. Epub 2011 Jan 24.
Abstract
The enantiomeric 2-azapinanes, aza analogues of the pinyl carbocation intermediates in pinene biosynthesis, were synthesized from (-)- and (+)-cis-pinonic acids. The individual reactions in the 5-step sequence were Beckmann rearrangement of the pinonic acid oximes, cyclization to the N-acetyl lactams, hydrolysis to the NH-lactams, N-methylations, and LiAlH(4) reductions. The anti stereochemistry of the N-methyl groups in the salts with respect to the gem-dimethyl bridge was established by NOE measurements and by X-ray diffraction analysis.
摘要
（手性）2-氮杂蒎烷是蒎烯生物合成中烯丙基碳正离子中间体的氮类似物，可由（-）-和（+）-顺式-蒎酸合成得到。该 5 步序列中的各个反应分别为：蒎酸肟的贝克曼重排、环化成 N-乙酰内酰胺、水解成 NH-内酰胺、N-甲基化和 LiAlH(4)还原。通过 NOE 测量和 X 射线衍射分析确定了盐中 N-甲基相对于偕二甲基桥的反立体化学。
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