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. 2018 Oct 5;8(10):8987-8992.
doi: 10.1021/acscatal.8b02717. Epub 2018 Aug 24.

Practical Intermolecular Hydroarylation of Terminal Alkenes via Reductive Heck Coupling

John A Gurak  1 , Keary M Engle  1
Affiliations

Practical Intermolecular Hydroarylation of Terminal Alkenes via Reductive Heck Coupling

John A Gurak et al. ACS Catal. .

Abstract

The hydroarylation of alkenes is an attractive approach to construct carbon-carbon (C-C) bonds from abundant and structurally diverse starting materials. Herein we report a palladiumcatalyzed reductive Heck hydroarylation of unactivated and heteroatom-substituted terminal alkenes with an array of (hetero)aryl iodides. The reaction is anti-Markovnikov selective and tolerates a wide variety of functional groups on both the alkene and (hetero)aryl coupling partners. Additionally, applications of this method to complex molecule diversifications were demonstrated. Deuteriumlabeling experiments are consistent with a mechanism in which the key alkylpalladium(II) intermediate is intercepted with formate and undergoes a decarboxylation/C-H reductive elimination cascade to afford the saturated product and turn over the cycle.

Keywords: Heck reaction; alkenes; hydroarylation; palladium; regioselectivity.

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Figures

Scheme 1.
Scheme 1.
Strategy and early precedents for the reductive Heck reaction.
Scheme 2.
Scheme 2.
Proposed catalytic cycle.
See this image and copyright information in PMC

References

    1. For selected reviews on the Heck reaction, see:Beletskaya IP, Cheprakov AV, Chem. Rev 2000, 100, 3009–3066; - PubMed
    2. Felpin F-X, Nassar-Hardy L, Le Callonnec F, Fouquet E, Tetrahedron 2011, 67, 2815–2831;
    3. Mc Cartney D, Guiry PJ, Chem. Soc. Rev 2011, 40, 5122–5150. - PubMed
    1. Liu Z, Derosa J, Engle KM, J. Am. Chem. Soc 2016, 138, 13076–13081. - PubMed
    1. Matsuura R, Jankins TC, Yang KS, Gallego GM, Yang S, He M, Wang F, Marsters R, McAlpine I, Engle KM, ChemRxiv 2018, DOI: 10.26434/chemrxiv.5885203. - DOI - PMC - PubMed
    1. For a review on early work, see: Cacchi S, Pure Appl. Chem 1990, 62, 713–722.
    1. Catellani M, Chiusoli GP, Giroldini W, Salerno G, J. Organomet. Chem 1980, 199, C21–C23;
    2. Arcadi A, Marinelli F, Bernocchi E, Cacchi S, Ortar G, J. Organomet. Chem 1989, 368, 249–256.