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Preparation of Alkynes: Alkylation Reaction

Preparation of Alkynes: Alkylation Reaction

Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.

Alkylation of β-Diester Enolates: Malonic Ester Synthesis

Alkylation of β-Diester Enolates: Malonic Ester Synthesis

Malonic ester synthesis is a method to obtain α substituted carboxylic acids from ꞵ-diesters such as diethyl malonate and alkyl halides.

Preparation of Alkynes: Dehydrohalogenation

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 to Carboxylic Acids: Oxidative Cleavage

Alkynes to Carboxylic Acids: Oxidative Cleavage

Alkynes undergo oxidative cleavage in the presence of oxidizing reagents like potassium permanganate and ozone. The triple bond — one σ bond and two π bonds — is completely cleaved, and the alkyne is oxidized to carboxylic acids. When warm and basic aqueous potassium permanganate is used as an oxidizing agent, alkynes are first converted to carboxylate salts via an unstable α-diketone intermediate. Further, a mild acid treatment protonates the carboxylate anions...

Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis

Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis

Acetoacetic ester synthesis is a method to obtain ketones from alkyl halides and β-keto esters. The reaction occurs in the presence of an alkoxide base that abstracts the acidic proton of the β-keto esters. The step results in an enolate ion which is doubly stabilized. The enolate then reacts with an alkyl halide via the SN2 process to produce an alkylated ester intermediate with a new C–C bond. The hydrolysis of the intermediate, followed by acidification, results in an...

α-Alkylation of Ketones via Enolate Ions

α-Alkylation of Ketones via Enolate Ions

Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...

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Related Experiment Video

Updated: Feb 28, 2026

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

Decarboxylative Alkynylation.

Joel M Smith¹, Tian Qin¹, Rohan R Merchant¹

¹The Scripps Research Institute (TSRI), North Torrey Pines Road, La Jolla, CA, 92037, USA.

Angewandte Chemie (International Ed. in English)

|June 22, 2017

Summary

This summary is machine-generated.

A novel decarboxylative cross-coupling method enables alkyne synthesis from carboxylic acids using nickel or iron catalysts. This efficient process, utilizing N-hydroxytetrachlorophthalimide esters, offers a scalable route to valuable synthetic intermediates.

Keywords:

alkynylation homologation iron catalysis nickel catalysis redox-active esters

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Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

Metal-free Synthesis of Ynones from Acyl Chlorides and Potassium Alkynyltrifluoroborate Salts

Published on: February 24, 2015

Area of Science:

Organic Chemistry
Catalysis
Synthetic Methodology

Background:

Carboxylic acids are versatile starting materials in organic synthesis.
Efficient methods for alkyne synthesis are crucial for constructing complex organic molecules.
Existing alkyne synthesis methods may have limitations in scope, scalability, or reagent availability.

Purpose of the Study:

To develop a new decarboxylative cross-coupling reaction for synthesizing terminal and substituted alkynes.
To explore the use of nickel- and iron-based catalysts for this transformation.
To establish a practical and scalable method for alkyne synthesis from carboxylic acids.

Main Methods:

Utilized nickel- and iron-based catalysts for decarboxylative cross-coupling.
Employed N-hydroxytetrachlorophthalimide (TCNHPI) esters for efficient carboxylic acid activation.
Incorporated an inexpensive, commercially available alkyne source in a formal homologation process.

Main Results:

Successfully synthesized terminal and substituted alkynes from various carboxylic acids.
Demonstrated the crucial role of TCNHPI esters in the reaction's success.
Showcased the reaction's amenability to in situ carboxylic acid activation.
Achieved a broad scope and operational simplicity in the alkyne synthesis.

Conclusions:

Developed a novel and efficient decarboxylative cross-coupling method for alkyne synthesis.
The method provides a scalable and practical alternative to existing alkyne synthesis strategies.
This transformation offers succinct routes to valuable synthetic intermediates.