从纯的H-mentylphosphinates中大量的光学活性P-类固醇酸
David Gatineau1, Laurent Giordano, Gérard Buono
1Equipe Chirosciences, UMR CNRS 6263-ISM2 Université Aix-Marseille III, Ecole Centrale de Marseille Av. Escadrille Normandie Niemen, 13397 Marseille Cedex 20, France.
Journal of the American Chemical Society
|June 18, 2011
概括
研究人员将薄荷酸盐转化为奇拉酸,从而能够合成体积大,具有高反体纯度的P-类固醇酸. 这种方法产生了受阻的三级胺和一种罕见的酸盐循环.
科学领域:
- 有机化学化学 有机化学
- 不对称的合成方法
- 立体化学是一种立体化学.
背景情况:
- 化素是不对称催化中的关键配体.
- 开发高效的方法来合成enantiopure大容量氨酸仍然是一个挑战.
研究的目的:
- 开发一种用于合成重P-类固醇二级和三级氨酸的新途径.
- 为了证明这些氨基在制备复杂的性有机金属化合物的实用性.
主要方法:
- 纯甲酸酸盐的转化为的酸酸.
- 将其加工成二级和三级氨酸.
- 一个酸盐循环的合成使用重的o-tolylphosphines.
主要成果:
- 成功制备了重的P-类固醇二次氨酸.
- 合成了各种各样的受阻的P-奇拉三级氨基酸,具有出色的反体过量.
- 通过合成一种罕见的enantiopure酸盐循环来说明实用性.
结论:
- 开发的方法提供了获取有价值的性氨酸基构建块的机会.
- 大量的P-奇拉酸是构建复杂的奇拉分子的有效连接体.
相关概念视频
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.
Hydroboration-Oxidation of Alkenes
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Hybridization of Atomic Orbitals I
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
Hybridization of Atomic Orbitals II
sp3d and sp3d 2 Hybridization
Regioselectivity of Electrophilic Additions-Peroxide Effect
In the presence of organic peroxides, the addition of hydrogen bromide to an alkene yields the isomer that is not predicted by Markovnikov’s rule. For example, the addition of hydrogen bromide to 2-methylpropene in the presence of peroxides gives 1-bromo-2-methylpropane. This addition reaction proceeds via a free radical mechanism, which reverses the regioselectivity. The free radical reaction mechanism involves three stages: initiation, propagation, and termination.

