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通过化物抽象氧化催化:使用偏磁放松增强NMR的方法开发和机制研究

  • 0Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14853, United States.

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Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide 02:44

9.9K

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.

Syn Dihydroxylation Mechanism
The reaction comprises a two-step mechanism. It begins with the addition of osmium tetroxide across the alkene double bond in a concerted manner forming a...

Oxymercuration-Reduction of Alkenes 02:36

7.4K

Oxymercuration–reduction of alkenes is one of the major reactions converting alkenes to alcohols. It involves the hydration of alkenes with mercuric acetate in a mixture of tetrahydrofuran and water, forming an organomercury adduct. This is followed by a demercuration step in which the adduct is reduced to an alcohol using sodium borohydride.

In the mixture of water and tetrahydrofuran, tetrahydrofuran acts as a solvent dissolving the alkene and the aqueous mercuric acetate solution, while...

Preparation of Amines: Reduction of Oximes and Nitro Compounds 01:29

3.4K

Oximes can be reduced to primary amines using catalytic hydrogenation, hydride reduction, or sodium metal reduction. The reduction of aliphatic and aromatic nitro compounds to primary amines takes place by either catalytic hydrogenation or by using active metals like Fe, Zn, and Sn in the presence of an acid.
Though catalytic hydrogenation can reduce nitrobenzenes, the reduction is nonselective in the presence of other functional groups. For instance, if nitrobenzene contains an aldehyde group,...

Aldehydes and Ketones with Amines: Enamine Formation Mechanism 01:14

5.3K

Enamine formation involves the addition of carbonyl compounds to a secondary amine through a series of reactions. The mechanism begins with the generation of carbinolamine, a nucleophilic attack followed by several proton transfer reactions. The hydroxyl group of the carbinolamine is converted into water to make a better leaving group that can push the reaction forward by eliminating a water molecule. In enamine formation, the last step involves the abstraction of a proton from the α carbon to...

Autoxidation of Ethers to Peroxides and Hydroperoxides 02:23

7.4K

Ethers represent a class of chemical compounds that become more dangerous with prolonged storage because they tend to form explosive peroxides when standing in the air. Autoxidation is the spontaneous oxidation of a compound in air. In the presence of oxygen, ethers slowly oxidize to form hydroperoxides and dialkyl peroxides.

If concentrated or heated, these peroxides may explode. Hence, ethers should be obtained in small quantities, kept in tightly sealed containers, and used promptly to...

Reduction of Alkynes to <em data-lazy-src=

9.1K

Alkynes can be reduced to trans-alkenes using sodium or lithium in liquid ammonia. The reaction, known as dissolving metal reduction, proceeds with an anti addition of hydrogen across the carbon–carbon triple bond to form the trans product. Since ammonia exists as a gas (bp = −33°C) at room temperature, the reaction is carried out at low temperatures using a mixture of dry ice (sublimes at −78°C) and acetone. 
When dissolved in liquid ammonia, an alkali metal,...