(+) -cis-sylvaticin的总合成:由催化剂催化的双氧化循环反应
Timothy J Donohoe1, Robert M Harris, Jeremy Burrows
1Department of Chemistry, University of Oxford, Chemistry Research Laboratory, UK. timothy.donohoe@chem.ox.ac.uk
Journal of the American Chemical Society
|October 19, 2006
概括
研究人员开发了一个简洁的合成cis-sylvaticin,一种天然产品. 这种方法利用二氧化二烯的双氧化循环,有效地用cis-tetrahydrofuran单元构建复杂分子.
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
- 催化剂是一种催化剂.
背景情况:
- 复杂的天然产品的合成往往需要创新的化学策略.
- cis-Tetrahydrofuran (cis-THF) 单元是生物活性分子中常见的结构动图.
- 构建双环系统的高效方法在合成化学中非常受欢迎.
研究的目的:
- 开发一种简洁而高效的合成途径,以获得天然产品cis-sylvaticin.
- 通过总合成来确认cis-sylvaticin的结构.
- 探索双氧化循环化在构建含有 cis-THF 的天然产品中的实用性.
主要方法:
- 采用了一种双降解/双氧化循环化策略.
- 催化四氧化物被用作氧化循环的关键试剂.
- 合成涉及一系列13个线性步骤和19个化学操作.
主要成果:
- 我们成功地构建了cis-sylvaticin的双环核.
- 自然产品的结构通过全合成得到证实.
- 一个非常简洁的合成路径到cis-sylvaticin是实现的.
结论:
- 双氧化二烯循环是用cis-THF单元合成天然产品的强大方法.
- 开发的战略提供了一个高效和简短的路线到cis-sylvaticin,确认其结构.
- 这项工作突出了催化四氧化在复杂分子合成中的潜力.
相关概念视频
SN2 Reaction: Stereochemistry
In an SN2 reaction, the nucleophilic attack on the substrate and departure of the leaving group occurs simultaneously through a transition state. As the nucleophile approaches the substrate from the back-side, the configuration of the substrate carbon changes from tetrahedral to trigonal bipyramidal and then back to tetrahedral, leading to an inversion in the configuration of the product.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
If the substrate is an achiral molecule at the α-carbon, the inversion of configuration is not observed.
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.
Preparation of Epoxides
Overview
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...
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.
Photochemical Electrocyclic Reactions: Stereochemistry
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
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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