通过二聚体选择性螺旋循环化完全替代的碳中心:对 (+) - 勒帕迪福明C的选择性合成
Matthew A Perry1, Matthew D Morin, Brian W Slafer
1Department of Chemistry, 1102 Natural Sciences II, University of California, Irvine, California 92697-2025, USA.
Journal of the American Chemical Society
|June 29, 2010
概括
减少N-Bocα-氨基烯酸的化产生具有惊人的选择性的α-氨基基试剂. 这种立体选择方法可以合成复杂的螺旋化合物和天然产品,如勒帕迪福明C.
科学领域:
- 有机化学 有机化学
- 立体选择性合成 立体选择性合成
背景情况:
- N-Bocα-氨基烯酸是有机合成中的多功能前体.
- 了解还原性化所产生的立体化学结果对于控制分子结构至关重要.
研究的目的:
- 为了研究N-Bocαααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααααα.
- 探索生成的α-氨基基试剂在循环反应中的应用.
- 为了实现立体选择性合成勒帕迪福明C.
主要方法:
- 减少N-Bocα-氨基烯酸的化.
- 分析中间根形状和A(1,3) - 菌株效应.
- 阿尔法-氨基基试剂的循环化与绑定的电友.
- 产品的立体化学分析.
主要成果:
- 减少性化过程具有意想不到的选择性,有利于在环素环中扭转配置.
- 基中间体与电友的循环还发生在反转过程中,导致整体保持配置.
- 由于不同的中间几何形状,α-氧-基循环表现出在两个步骤中的保留.
- 开发的方法被应用于简短的合成勒帕迪福明C.
结论:
- 降解性化所产生的立体化学结果是由与单一对和A(1,3) - 菌株效应的激进对齐所决定的.
- 阿尔法胺基螺旋循环化提供了一个强大的工具,用于构建复杂的循环结构与受控的立体化学.
- 这种方法为自然产品的立体选择性合成提供了一个新的途径.
相关概念视频
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.
Cycloaddition Reactions: Overview
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
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