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Updated: Jun 5, 2025

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

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Published on: June 21, 2017

An Untethered and Formal Intermolecular Hexadehydro-Diels-Alder Reaction: Alkynylboronates with

Trinadh Kaicharla¹, Mengyuan Jin¹, Thomas R Hoye¹

¹Department of Chemistry, University of Minnesota, 207 Pleasant St., SE, Minneapolis, Minnesota 55455, United States.

Journal of the American Chemical Society

|December 6, 2024

Abstract:

We show that 2-diynylpyridine and a Bpin-terminated monoyne or diyne will cross-react to form benzyne intermediates. These reactive intermediates are captured by various in situ trapping agents to give products of three-component reactions. Various control reactions, substrate modification, binding studies, and DFT analysis suggest that a small amount of a noncovalent Lewis acid-base complex is the active species within which the diyne and diynophile engage to produce the benzyne. Only a single isomeric benzyne is formed when a Bpin-diyne is used; this selectivity is rationalized by the geometric distortion seen in the DFT-computed diradical intermediate.

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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.

Diels–Alder Reaction Forming Cyclic Products: Stereochemistry

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The Diels–Alder reaction is one of the robust methods for synthesizing unsaturated six-membered rings. The reaction involves a concerted cyclic movement of six π electrons: four π electrons from the diene and two π electrons from the dienophile.

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In a Diels–Alder reaction, the diene is usually an electron-rich system and acts as a nucleophile, whereas the dienophile is electron-deficient and functions as an electrophile. Much like the diene, the nature of the dienophile significantly impacts the outcome of the reaction.
Characteristics of Dienophiles
Generally, the best dienophiles are alkenes containing electron-withdrawing substituents such as carbonyl, nitrile, and nitro groups. The feasibility of a Diels–Alder reaction depends...

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

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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.

Hydroboration-Oxidation of Alkenes

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.

Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

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Diels–Alder reactions between cyclic dienes locked in an s-cis configuration and dienophiles yield bridged bicyclic products.

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