一个简洁的enantioselective合成的chlorosulfolipid malhamensilipin一个简洁的A合成
D Karl Bedke1, Grant M Shibuya, Alban R Pereira
1Department of Chemistry, University of California, Irvine, California 92697, USA.
Journal of the American Chemical Society
|February 10, 2010
概括
研究人员报告了第一个malhamensilipin A的enantioselective合成,这是一个硫脂类天然产物. 这项研究强调了对极地群体的立体选择性引入和形成独特的乙烯硫酸盐部分.
科学领域:
- 有机化学 有机化学
- 自然产品的合成自然产品的合成
- 立体选择性合成 立体选择性合成
背景情况:
- 硫脂是一种具有复杂结构的自然产品.
- 马尔哈门西利平A是这个家族的显著成员,以前缺乏明确的合成路径.
研究的目的:
- 为了实现第一个马尔汉梅西利平A.的酶选择性合成,A.
- 研究用于引入极替代剂的立体选择方法.
- 为了阐明独特的 (E) - 乙烯硫酸盐组的形成机制.
主要方法:
- 使用了对抗选择性合成策略.
- 两极函数组的立体选择性引入.
- 化学,区域和立体选择性E2消除反应被用于乙烯硫酸盐的形成.
主要成果:
- 马尔汉森利平A的成功的选择性合成.
- 所有极替代剂都实现了高立体选择性.
- (E) - 乙烯硫酸盐是通过选择性E2消除HCl合成的.
结论:
- 开发的合成途径提供了对马尔汉梅西利平A的获取.
- 这项研究提供了对硫脂的潜在生物合成途径的见解.
- 该方法适用于合成相关的自然产品.
相关概念视频
Alkylation of β-Diester Enolates: Malonic Ester Synthesis
Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.
Preparation and Reactions of Sulfides
Sulfides are the sulfur analog of ethers, just as thiols are the sulfur analog of alcohol. Like ethers, sulfides also consist of two hydrocarbon groups bonded to the central sulfur atom. Depending upon the type of groups present, sulfides can be symmetrical or asymmetrical. Symmetrical sulfides can be prepared via an SN2 reaction between 2 equivalents of an alkyl halide and one equivalent of sodium sulfide.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
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...
Sharpless Epoxidation
The conversion of allylic alcohols into epoxides using the chiral catalyst was discovered by K. Barry Sharpless and is known as Sharpless epoxidation. The use of a chiral catalyst enables the formation of one enantiomer of the product in excess. This chiral catalyst is mainly a chiral complex of titanium tetraisopropoxide and tartrate ester (specific stereoisomer). The stereoisomer used in the chiral catalyst dictates the formation of the enantiomer of the product. In other words, the use of...
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
Formation of Halohydrin from Alkenes
An alkene, such as propene, reacts with bromine in the presence of water to yield a halohydrin. Halohydrins contain a halogen and a hydroxyl group attached to adjacent carbons. When the halogen is bromine, it is called a bromohydrin, while a chlorohydrin has chlorine as the halogen.

