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
. 2012 Oct 3;134(39):16131-4.
doi: 10.1021/ja306446m. Epub 2012 Sep 19.

Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration

R David Grigg  1 , Ryan Van Hoveln, Jennifer M Schomaker
Affiliations

Copper-catalyzed recycling of halogen activating groups via 1,3-halogen migration

R David Grigg et al. J Am Chem Soc. .

Abstract

A Cu(I)-catalyzed 1,3-halogen migration reaction effectively recycles an activating group by transferring bromine or iodine from a sp(2) to a benzylic carbon with concomitant borylation of the Ar-X bond. The resulting benzyl halide can be reacted in the same vessel under a variety of conditions to form an additional carbon-heteroatom bond. Cross-over experiments using an isotopically enriched bromide source support intramolecular transfer of Br. The reaction is postulated to proceed via a Markovnikov hydrocupration of the o-halostyrene, oxidative addition of the resulting Cu(I) complex into the Ar-X bond, reductive elimination of the new sp(3) C-X bond, and final borylation of an Ar-Cu(I) species to turn over the catalytic cycle.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Traditional cross-coupling approach vs. a new mode of arene functionalization.
Scheme 2
Scheme 2
Recycling of the activating group.
Scheme 3
Scheme 3
Cross-over experiment using isotopically enriched 79Br.
Scheme 4
Scheme 4
A potential mechanism for the Cu-catalyzed 1,3-halogen migration.
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

See all "Cited by" articles

References

    1. Negishi Ei, de Meijere A., editors. Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley; New York: 2002.
    2. de Meijere A, Diederich F, editors. Metal-Catalyzed Cross-Coupling Reactions. 2nd. Wiley-VCH; Weinheim: 2004.

    1. Selected reviews of C-H functionalization: Mkhalid IA, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem Rev. 2010;110:890.Lyons TW, Sanford MS. Chem Rev. 2010;110:1147.Engle KM, Mei TS, Wasa M, Yu JQ. Acc Chem Res. 2012;45:788.Neufeldt SR, Sanford MS. Acc Chem Res. 2012;45:936.Song G, Wang F, Li X. Chem Soc Rev. 2012;41:3651.Ackermann L. Chem Rev. 2011;111:1315.Davies HML, Morton D. Chem Soc Rev. 2011;40:1857.Wendlandt AE, Suess AM, Stahl SS. Angew Chem Int Ed. 2011;50:11062.

    1. Bedford RB, Coles SJ, Hursthouse MB, Limmert ME. Angew Chem Int Ed. 2003;42:112. - PubMed
    2. Ihara H, Suginome M. J Am Chem Soc. 2009;131:7502. - PubMed
    3. Robbins DW, Boebel TA, Hartwig JF. J Am Chem Soc. 2010;132:4068. - PubMed
    4. Dai HX, Stepan AF, Plummer MF, Zhang YH, Yu JQ. J Am Chem Soc. 2011;133:7222. - PubMed
    5. Huang C, Chattopadhyay B, Grevorgyan V. J Am Chem Soc. 2011;133:12406. - PMC - PubMed
    6. Gulevich AV, Melkonyan FS, Sarkar D, Gevorgyan V. J Am Chem Soc. 2012;134:5528. - PMC - PubMed

    1. Recent examples of activating group recycling: Newman SG, Lautens M. J Am Chem Soc. 2011;133:1778.Hooper JF, Chaplin AB, González-Rodríguez C, Thompson AL, Weller AS, Willis MC. J Am Chem Soc. 2012;134:2906.

    1. Noh D, Chea H, Ju J, Yun J. Angew Chem Int Ed. 2009;48:6062. - PubMed
    2. Noh D, Yoon SK, Won J, Lee JY, Yun J. Chem Asian J. 2011;6:1967. - PubMed
    3. Won J, Noh D, Yun J, Lee JY. J Phys Chem A. 2010;114:12112. - PubMed

Publication types