Synfacts 2022; 18(08): 0905
DOI: 10.1055/s-0041-1737718
Organo- and Biocatalysis

Light-Initiated Hydrogen Atom Transfer-Driven Asymmetric Minisci Reaction of Primary Alcohols

Rezensent(en):
Benjamin List
,
Luc M. Debie
Colgan AC, Proctor RS. J, Gibson DC, Chuentragool P, Lahdenperä AS. K, Ermanis K, *, Phipps RJ. * University of Cambridge and University of Nottingham, UK
Hydrogen Atom Transfer Driven Enantioselective Minisci Reaction of Alcohols.

Angew. Chem. Int. Ed. 2022;
61: e202200266
DOI: 10.1002/anie.202200266.
 

Significance

Ermanis, Phipps, and co-workers report a light-initiated, hydrogen atom transfer (HAT)-driven asymmetric Minisci reaction of primary alcohols with pyridines. The reaction proceeds through an α-hydroxy radical intermediate formed by α-hydrogen atom abstraction from the alcohol by dicumyl peroxide (DCP) upon irradiation. The resulting hydroxyalkylated pyridines are obtained in moderate yields and with good to excellent enantio­selectivities. The reaction is selective to the C2 position of the pyridine and tolerates alkyl functionalization on every position of the pyridine, as well as a variety of functional handles on the primary alcohol.


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Comment

The currently reported formal dehydrogenative C–H to C–H bond coupling expands upon the authors’ previously reported Minisci reaction between N-heterocycles and α-imido radicals generated in situ (Science 2018, 360, 419) by eliminating the requirement for a protected amine to form the α-radical. The addition of unprotected feedstock alcohols to the scope of this type of reactivity presents a significant advance in its utility. We look forward to potential modifications of this methodology that would optimize the yield.


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Publikationsverlauf

Artikel online veröffentlicht:
18. Juli 2022

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