来自终端基因的不对称合成,通过滴解和交叉合的级联
Scott N Mlynarski1, Christopher H Schuster1, James P Morken1
1Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
Nature
|December 20, 2013
概括
这项研究引入了一种新的催化方法,用于从简单的基因中制造奇拉分子. 单瓶反应有效地将终端基转化为具有高选择性的有价值的性产品.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 终端基因是有机合成中的多功能起始材料,因为它们的稳定性和大规模可用性.
- 很少有催化酶选择性方法可以将异形α-olefins转化为具有高反体过剩 (> 90%) 的奇拉产品.
- 现有的方法往往缺乏在终端碳的链延长碳-碳键形成.
研究的目的:
- 开发一种新型的催化酶选择策略,用于直接将终端基因转化为奇拉产品.
- 为了解决当前合成方法的局限性,以功能化α-olefins.
- 为了使各种奇拉醇和氨基的合成不易通过其他方式获得.
主要方法:
- 开发了一种单瓶,并联的二酸化/交叉合反应.
- 催化1,2-bis (酸) 的交叉合是由一个邻近的功能组促进的.
- 使用终端基的抗选择性二解法.
主要成果:
- 开发的方法实现了高收益率和高选择性 (>95: 5反体比) 合产品.
- 商用催化剂和试剂的低催化剂负载 (1-2 mol%) 被使用.
- 反应表现出一个广的基质范围,使得各种性酒精和氨基的合成.
结论:
- 这一策略为从终端基因中生成的奇拉产品的催化酶选择合成提供了直接和有效的途径.
- 双重二氧化/交叉合反应克服了来自α-olefins的奇拉合成之前的局限性.
- 该方法提供了一个通用的平台,可以访问广泛的有价值的性分子.
相关概念视频
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
8.0K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
8.0K
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry
4.3K
Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.
4.3K
Diels–Alder Reaction Forming Cyclic Products: Stereochemistry
3.1K
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.
3.1K
Cycloaddition Reactions: Overview
2.4K
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.
2.4K
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
1.4K
The radical dimerization of ketones or aldehydes gives vicinal diols through a pinacol coupling reaction. However, the behavior of titanium metals used for the reaction as a source of electrons is unusual. When the reaction is carried out in the presence of titanium, diols can be isolated at low temperatures. Else titanium further reacts with diols, forming alkenes through the McMurry reaction.
1.4K
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
2.6K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
2.6K


