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铜催化选择性C ((sp3) -H化使用亚基醇衍生物作为调解剂

  • 0College of Pharmacy, Nanjing University of Chinese Medicine, Nanjing 210000, People's Republic of China.

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Preparation of 1° Amines: Azide Synthesis 01:22

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Direct alkylation of ammonia produces polyalkylated amines, along with a quaternary ammonium salt. To exclusively prepare primary amines, the azide synthesis method can be used.
Azide ions act as good nucleophiles and react with unhindered alkyl halides to form alkyl azides. Alkyl azides do not participate in further nucleophilic substitution reactions, thereby eliminating the chances of polyalkylated products. Alkyl azides are reduced by hydride-based reducing agents, like lithium aluminum...

Preparation of Epoxides 03:00

8.1K

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...

Aldol Condensation with β-Diesters: Knoevenagel Condensation 01:27

3.2K

The Knoevenagel condensation is an aldol-type reaction involving the condensation of aldehydes or ketones with active methylene compounds such as β-diesters to produce substituted olefins.

The reaction is catalyzed by amine base, which abstracts the acidic α hydrogen of the activated methylene to generate a resonance stabilized enolate ion. The basic strength of the amine is insufficient to form the enolate of aldehydes or ketones. However, it acts as a nucleophile that attacks the carbonyl...

Esters to β-Ketoesters: Claisen Condensation Mechanism 01:08

3.8K

Regular Claisen condensation involves the synthesis of β-ketoesters by combining identical ester molecules bearing two α hydrogens in the presence of an alkoxide base. The reaction commences with the deprotonation of the acidic α hydrogen by the base to form a resonance stabilized ester enolate. This nucleophilic ion then attacks the carbonyl center of another ester molecule to generate a tetrahedral alkoxide intermediate. Next, the expulsion of the alkoxide group from the...

Carboxylic Acids to Methylesters: Alkylation using Diazomethane 01:33

2.4K

Carboxylic acids react with diazomethane in an ether solvent via alkylation at the carboxylate oxygen atom to give methyl esters of the corresponding acid with excellent yields.

Diazomethane is a yellow gas having a boiling point of −23 °C. It is conveniently prepared by the action of a base on N-methyl-N-nitrosourea or N-methyl-N-nitrosotoluenesulphonamide.
The esterification mechanism involves the protonation of diazomethane by the carboxylic acid to yield a carboxylate salt and...

Acid Halides to Esters: Alcoholysis 01:12

3.1K

Alcoholysis is a nucleophilic acyl substitution reaction in which an alcohol functions as a nucleophile. Acid halides react with alcohol to produce esters. The mechanism proceeds in three steps:

First, the alcohol acts as a nucleophile and attacks the acyl carbon to form a tetrahedral intermediate.
Next, the carbonyl re-forms with the loss of a chloride ion.
Lastly, the positively charged intermediate loses a proton to give an ester as the final product along with H3O+, making HCl an...