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 6 2021
Accepted
06 7 2021
First published
06 7 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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