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. 2023 Jan 23;62(4):e202214153.
doi: 10.1002/anie.202214153. Epub 2022 Dec 15.

A Sterically Tuned Directing Auxiliary Promotes Catalytic 1,2-Carbofluorination of Alkenyl Carbonyl Compounds

Zhonglin Liu  1 , Lucas J Oxtoby  1 , Juntao Sun  1 , Zi-Qi Li  1 , Nana Kim  1 , Geraint H M Davies  2 , Keary M Engle  1
Affiliations

A Sterically Tuned Directing Auxiliary Promotes Catalytic 1,2-Carbofluorination of Alkenyl Carbonyl Compounds

Zhonglin Liu et al. Angew Chem Int Ed Engl. .

Abstract

The site-selective palladium-catalyzed three-component coupling of unactivated alkenyl carbonyl compounds, aryl- or alkenylboronic acids, and N-fluorobenzenesulfonimide is described herein. Tuning of the steric environment on the bidentate directing auxiliary enhances regioselectivity and facilitates challenging C(sp3 )-F reductive elimination from a PdIV intermediate to afford 1,2-carbofluorination products in moderate to good yields.

Keywords: Alkene Functionalization; Cross-Coupling; Directing Group; Fluorination; Palladium.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
a) State of the art in palladium‐catalyzed alkene arylfluorination using electronic control. b) Recent examples in palladium‐catalyzed alkene arylfluorination using directing groups. c) Directed carbofluorination utilizing a novel directing group for alkene functionalization.
Scheme 2
Scheme 2
Correlation between selectivity/yield and the percentage of buried volume, %VBur, (the fraction of the volume of a sphere centered on the palladium atom occupied by a given ligand, or in this case, directing group) calculated for AQ, PIP, and PDE; (L1=N(SO2Ph)2, L2=MeCN).
Scheme 3
Scheme 3
Proposed catalytic cycle.
Scheme 4
Scheme 4
Extension to enantioselective 1,2‐arylfluorination.
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