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
. 2017 Jun 1;56(23):6651-6654.
doi: 10.1002/anie.201703089. Epub 2017 May 3.

Palladium-Catalyzed Enantioselective Redox-Relay Heck Alkynylation of Alkenols To Access Propargylic Stereocenters

Zhi-Min Chen  1 , Christine S Nervig  1 , Ryan J DeLuca  1 , Matthew S Sigman  1
Affiliations

Palladium-Catalyzed Enantioselective Redox-Relay Heck Alkynylation of Alkenols To Access Propargylic Stereocenters

Zhi-Min Chen et al. Angew Chem Int Ed Engl. .

Abstract

An enantioselective redox-relay Heck alkynylation of di- and trisubstituted alkenols to construct propargylic stereocenters is disclosed using a new pyridine oxazoline ligand. This strategy allows direct access to chiral β-alkynyl carbonyl compounds employing allylic alcohol substrates in contrast to more traditional conjugate addition methods.

Keywords: Heck reaction; alkenes; alkynylation; propargylic stereocenter.

PubMed Disclaimer

Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Proposed redox-relay Heck alkynylation to access propargylic stereocenters.
Scheme 2
Scheme 2
Deuterium Labeling Study.
See this image and copyright information in PMC

References

    1. For selected reviews, see:

    2. Heck RF. Acc Chem Res. 1979;12:146–151.
    3. Crisp GT. Chem Soc Rev. 1998;27:427–436.
    4. Beletskaya IP, Cheprakov AV. Chem Rev. 2000;100:3009–3066. - PubMed
    5. Shibasaki M, Vogl EM, Ohshima T. Adv Synth Catal. 2004;346:1533–1552.
    6. Zeni G, Larock RC. Chem Rev. 2006;106:4644–4680. - PubMed
    7. Le Bras J, Muzart J. Chem Rev. 2011;111:1170–1214. - PubMed
    8. McCartney D, Guiry PJ. Chem Soc Rev. 2011;40:5122–5150. - PubMed
    9. Seechurn CCCJ, Kitching MO, Colacot TJ, Snieckus V. Angew Chem. 2012;124:5150–5174.
    10. Angew Chem Int Ed. 2012;51:5062–5085. - PubMed

    1. For selected works, see:

    2. Larock RC, Leung WY, Stolz-Dunn S. Tetrahedron Lett. 1989;30:6629–6632.
    3. Bouquillon S, Ganchegui B, Estrine B, Hénin F, Muzart J. J Organomet Chem. 2001;634:153–156.
    4. Berthiol F, Doucet H, Santelli M. Tetrahedron. 2006;62:4372–4383.
    5. Oliveira CC, Pfaltz A, Correia CRD. Angew Chem. 2015;127:14242–14245.
    6. Angew Chem Int Ed. 2015;54:14036–14039. - PubMed
    7. Singh S, Bruffaerts J, Vasseur A, Marek I. Nat Commun. 2017;8 doi: 10.1038/ncomms14200. - DOI - PMC - PubMed
    1. Werner EW, Mei TS, Burckle AJ, Sigman MS. Science. 2012;338:1455–1458. - PMC - PubMed
    1. Mei TS, Werner EW, Burckle AJ, Sigman MS. J Am Chem Soc. 2013;135:6830–6833. - PMC - PubMed
    2. Mei TS, Patel HH, Sigman MS. Nature. 2014;508:340–344. - PMC - PubMed
    3. Zhang C, Santiago CB, Kou L, Sigman MS. J Am Chem Soc. 2015;137:7290–7293. - PMC - PubMed
    4. Chen ZM, Hilton MJ, Sigman MS. J Am Chem Soc. 2016;138:11461–11464. - PMC - PubMed
    1. Patel HH, Sigman MS. J Am Chem Soc. 2015;137:3462–3465. - PMC - PubMed
    2. Patel HH, Sigman MS. J Am Chem Soc. 2016;138:14226–14229. - PMC - PubMed
    3. Zhang C, Tutkowski B, DeLuca RJ, Joyce LA, Wiest O, Sigman MS. Chem Sci. 2017;8:2277–2282. - PMC - PubMed

Publication types

LinkOut - more resources