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. 2025 Jan 10;27(1):241-245.
doi: 10.1021/acs.orglett.4c04260. Epub 2024 Dec 18.

A General Platform for Copper-Catalyzed Atom Transfer Radical Addition with Electron-Deficient Olefins

Hannah C Wendlandt  1 , Jacob A Utley  1 , Byung Joo Lee  1 , Tam D Ho  1 , Kami L Hull  1
Affiliations

A General Platform for Copper-Catalyzed Atom Transfer Radical Addition with Electron-Deficient Olefins

Hannah C Wendlandt et al. Org Lett. .

Abstract

We disclose a broad platform for copper-catalyzed atom transfer radical addition (ATRA) of electron-deficient olefins. Catalytic Cu(dtbbpy)2(OTf)2 enables radical addition of electron-deficient alkyl halides to acrylates, acrylamides, and vinyl sulfones in fair to excellent yields. The resultant ATRA products can be used in a variety of telescoped reactions, including substitution with basic amine nucleophiles to afford α-amino esters. The synthetic utility of the products is further demonstrated through derivatization to give substituted cyclopropanes and a γ,δ-unsaturated ester.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
Select previous examples of intermolecular ATRA
Scheme 2.
Scheme 2.. Scope of the Cu-Catalyzed ATRA.a
a Reactions run at 0.2 mmol scale in duplicate. b 20 mol % DIPEA in place of PhNHMe. c 2.0 mmol scale.
Scheme 3.
Scheme 3.. Synthetic Utilitya
aTelescoped reaction sequence run at 0.2 mmol scale in duplicate; d.r. confirmed by crude GC analysis. b2.0 mmol scale
Scheme 4.
Scheme 4.. Ramberg-Bäcklund Reaction
Isolated yield of product at 0.2 mmol scale. ain-situ yield determined by GC analysis of the crude reaction mixture.
See this image and copyright information in PMC

References

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