Issue 1, 2023

Hydrogen Bonding-directed Sequential 1,6/1,4-Addition of Heteroatom Nucleophiles onto Electron-deficient 1,3-Diynes

Abstract

A sequential inter- and intramolecular 1,6/1,4-addition on electron-deficient 1,3-diynes conjugated with a ketone, ester, or imide functionality is described. This tandem process is effectively directed by a propargylic –OH or –NH functionality. Alcohols, amines, and thiols show excellent reactivity for the initial 1,6-addition. The addition of amines occurs at ambient temperature, whereas other nucleophiles require high temperatures up to 100 °C and a base additive such as DABCO. Substrates with propargylic hydrogen undergo double bond isomerization at higher temperatures (70–100 °C) to form furan and pyrrole rings. Nonenolizable 1,3-diynones with an electron-withdrawing group provide good yields (72–86%) with most nucleophiles.

Graphical abstract: Hydrogen Bonding-directed Sequential 1,6/1,4-Addition of Heteroatom Nucleophiles onto Electron-deficient 1,3-Diynes

Supplementary files

Article information

Article type
Research Article
Submitted
31 Oct 2022
Accepted
20 Nov 2022
First published
29 Nov 2022

Org. Chem. Front., 2023,10, 209-215

Hydrogen Bonding-directed Sequential 1,6/1,4-Addition of Heteroatom Nucleophiles onto Electron-deficient 1,3-Diynes

E. Liyanage Perera and D. Lee, Org. Chem. Front., 2023, 10, 209 DOI: 10.1039/D2QO01730J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements