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
. 2010 Aug 18;132(32):11009-11.
doi: 10.1021/ja103838d.

Cu(I)-catalyzed regioselective diamination of conjugated dienes via dual mechanistic pathways

Baoguo Zhao  1 , Xingao Peng, Sunliang Cui, Yian Shi
Affiliations

Cu(I)-catalyzed regioselective diamination of conjugated dienes via dual mechanistic pathways

Baoguo Zhao et al. J Am Chem Soc. .

Abstract

This paper describes the Cu(I)-catalyzed regioselective diamination of conjugated dienes using di-tert-butyldiaziridinone as nitrogen source. The internal diamination and terminal diamination likely proceed via two mechanistic pathways. Various dienes can be efficiently diaminated at the internal double bonds with high regio- and diasteroselectivity in good yield using inexpensive CuBr as catalyst.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
Scheme 2
Scheme 2
Scheme 3
Scheme 3
Scheme 4
Scheme 4
Proposed dual mechanisms for the Cu(I)-catalyzed diamination of conjugated dienes
Scheme 5
Scheme 5
Addition of radical B to the internal double bond
See this image and copyright information in PMC

References

    1. For leading reviews, see: Lucet D, Gall TL, Mioskowski C. Angew. Chem., Int. Ed. 1998;37:2580.. Mortensen MS, O'Doherty GA. Chemtracts: Org. Chem. 2005;18:555.. Kotti SRSS, Timmons C, Li G. Chem. Biol. Drug Des. 2006;67:101.. Kizirian J-C. Chem. Rev. 2008;108:140.. Lin G-Q, Xu M-H, Zhong Y-W, Sun X-W. Acc. Chem. Res. 2008;41:831.. de Figueiredo RM. Angew. Chem., Int. Ed. 2009;48:1190.. Cardona F, Goti A. Nat. Chem. 2009;1:269..

    1. For examples of metal-mediated diaminations, see: Tl: Aranda VG, Barluenga J, Aznar F. Synthesis. 1974:504.. Os: Chong AO, Oshima K, Sharpless KB. J. Am. Chem. Soc. 1977;99:3420.. Muñiz K. Eur. J. Org. Chem. 2004:2243.. Pd: Bäckvall J-E. Tetrahedron Lett. 1978:163.. Hg: Barluenga J, Alonso-Cires L, Asensio G. Synthesis. 1979:962.. Co: Becker PN, White MA, Bergman RG. J. Am. Chem. Soc. 1980;102:5676.. Mn: Fristad WE, Brandvold TA, Peterson JR, Thompson SR. J. Org. Chem. 1985;50:3647..

    1. For recent Cu(II)-mediated intramolecular diamination, see: Zabawa TP, Kasi D, Chemler SR. J. Am. Chem. Soc. 2005;127:11250.. Zabawa TP, Chemler SR. Org. Lett. 2007;9:2035..

    1. For Rh(II), Cu(I), and Fe(III)-catalyzed diamination with TsNCl2 or TsNBr2, see: Li G, Wei H-X, Kim SH, Carducci MD. Angew. Chem., Int. Ed. 2001;40:4277.. Wei H-X, Kim SH, Li G. J. Org. Chem. 2002;67:4777.. Han J, Li T, Pan Y, Kattuboina A, Li G. Chem. Biol. Drug. Des. 2008;71:71..

    1. For a recent Au(I)-catalyzed intramolecular diamination of allenes via dihydroamination, see: Li H, Widenhoefer RA. Org. Lett. 2009;11:2671..

Publication types