通过双重不对称的诱导,通过对抗面选择性催化Allenes的化
Michinori Suginome1, Toshimichi Ohmura, Yoshihiro Miyake
1Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, and PRESTO, Japan Science and Technology Corporation (JST), Katsura, Nishikyo-ku, Kyoto 615-8510, Japan. suginome@sbchem.kyoto-u.ac.jp
Journal of the American Chemical Society
|October 14, 2005
概括
研究人员使用催化剂和性辅助剂合成了丰富的β-甲基. 这种方法实现了高立体选择性,为性有机化合物提供了新的途径.
科学领域:
- 有机金属化学 有机金属化学
- 不对称的合成方法
- 催化剂是一种催化剂.
背景情况:
- 性有机化合物是有机合成中有价值的构建模块.
- 为它们的立体选择性合成开发高效的方法仍然是一个挑战.
研究的目的:
- 开发一种新型的催化方法,用于合成丰富的β-玻利烯基.
- 探索在不对称的-键添加反应中使用奇拉辅助剂.
主要方法:
- 帕拉催化反表面-选择性添加-键到终端亚伦.
- 使用了一种化催化剂与一种性单酸酸连接体.
- 采用了在原子上具有奇拉辅助的西利波兰.
主要成果:
- 成功合成了富含抗原的β-玻里烯.
- 实现了高Enantio表面选择性,高达96%的脱离率.
- 证明了在控制立体化学方面性辅助的有效性.
结论:
- 开发的催化反应提供了一条有效的途径,以化β-玻利烯酸.
- 使用合辅助器对于实现高立体选择性至关重要.
- 这种方法扩大了有机化合物的不对称合成工具包.
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Introduction to Electrophilic Addition Reactions of Alkenes
The double bond in a simple, unconjugated alkene is a region of high electron density that can act as a weak base or a nucleophile. The filled π orbital (HOMO) of the double bond can interact with the empty LUMO of an electrophile. A bonding interaction occurs when the electrophile attacks between the two carbons; the electrophile then accepts a pair of electrons from the π bond and undergoes addition across the double bond, yielding a single product.
Addition and elimination reactions can be...
Addition and elimination reactions can be...
Halogenation of Alkenes
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Regioselectivity and Stereochemistry of Hydroboration
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Preparation of Alkynes: Dehydrohalogenation
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Electrophilic Addition to Alkynes: Halogenation
Introduction
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
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.


