Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2011 May 4;133(17):6541-4.
doi: 10.1021/ja2015586. Epub 2011 Apr 8.

Aerobic Pd-catalyzed sp3 C-H olefination: a route to both N-heterocyclic scaffolds and alkenes

Kara J Stowers  1 , Kevin C Fortner, Melanie S Sanford
Affiliations

Aerobic Pd-catalyzed sp3 C-H olefination: a route to both N-heterocyclic scaffolds and alkenes

Kara J Stowers et al. J Am Chem Soc. .

Abstract

This communication describes a new method for the Pd/polyoxometalate-catalyzed aerobic olefination of unactivated sp(3) C-H bonds. Nitrogen heterocycles serve as directing groups, and air is used as the terminal oxidant. The products undergo reversible intramolecular Michael addition, which protects the monoalkenylated product from overfunctionalization. Hydrogenation of the Michael adducts provides access to bicyclic nitrogen-containing scaffolds that are prevalent in alkaloid natural products. Additionally, the cationic Michael adducts undergo facile elimination to release α,β-unsaturated olefins, which can be further elaborated via C-C and C-heteroatom bond-forming reactions.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Reduction Reactions of 2
Scheme 2
Scheme 2
Functionalization of C–H Olefinated Product 15.a
See this image and copyright information in PMC

References

    1. Oestreich M, editor. The Mizoroki-Heck Reaction. John Wiley and Sons; Chicester, U.K.: 2009.
    1. Satoh T, Miura M. Chem. Eur. J. 2010;16:11212. - PubMed
    2. pp. 383–400. Ref 1.
    1. Trost BM, Godleski SA, Genet JP. J. Am. Chem. Soc. 1978;100:3930.
    2. Baran PS, Corey EJ. J. Am. Chem. Soc. 2002;124:7904. - PubMed
    3. Garg NK, Caspi DD, Stoltz BM. J. Am. Chem. Soc. 2004;126:9552. - PubMed
    4. Beck EM, Hatley R, Gaunt MJ. Angew. Chem. Int. Ed. 2008;47:3004. - PubMed
    5. Wang DH, Engle KM, Shi BF, Yu J-Q. Science. 2010;327:315. - PMC - PubMed
    1. pp. 345–378. Ref. 1.
    1. Wasa M, Engle KM, Yu JQ. J. Am. Chem. Soc. 2010;132:3680. - PMC - PubMed

Publication types