Issue 31, 2021

Radical hydroxymethylation of alkyl iodides using formaldehyde as a C1 synthon

Abstract

Radical hydroxymethylation using formaldehyde as a C1 synthon is challenging due to the reversible and endothermic nature of the addition process. Here we report a strategy that couples alkyl iodide building blocks with formaldehyde through the use of photocatalysis and a phosphine additive. Halogen-atom transfer (XAT) from α-aminoalkyl radicals is leveraged to convert the iodide into the corresponding open-shell species, while its following addition to formaldehyde is rendered irreversible by trapping the transient O-radical with PPh3. This event delivers a phosphoranyl radical that re-generates the alkyl radical and provides the hydroxymethylated product.

Graphical abstract: Radical hydroxymethylation of alkyl iodides using formaldehyde as a C1 synthon

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Jūn. 2021
Accepted
06 Jūl. 2021
First published
06 Jūl. 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2021,12, 10448-10454

Radical hydroxymethylation of alkyl iodides using formaldehyde as a C1 synthon

L. Caiger, C. Sinton, T. Constantin, J. J. Douglas, N. S. Sheikh, F. Juliá and D. Leonori, Chem. Sci., 2021, 12, 10448 DOI: 10.1039/D1SC03083C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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