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. 2011 Jan 1;696(1):150-158.
doi: 10.1016/j.jorganchem.2010.08.041.

Evolution of copper(II) as a new alkene amination promoter and catalyst

Sherry R Chemler  1
Affiliations

Evolution of copper(II) as a new alkene amination promoter and catalyst

Sherry R Chemler. J Organomet Chem. .

Abstract

Copper(II) carboxylates and chiral copper(II) triflate·bis(oxazoline) complexes promote and catalyze intramolecular alkene carboamination, diamination and aminooxygenation reactions, creating an array of nitrogen heterocycles. High diastereoselectivity and enantioselectivity can be achieved in these transformations. This account reviews the discovery and development of these useful and interesting reactions.

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Figures

Fig. 1
Fig. 1
Origin of 2,5-cis-diastereoselectivity with α-substituted substrates.
Fig. 2
Fig. 2
Other products, selectivities (see Eq. (14) for conditions).
Scheme 1
Scheme 1
Copper(II)-promoted intramolecular carboamination of N-arylsulfonyl-2-allylanilines.
Scheme 2
Scheme 2
Two initially proposed potential mechanisms for the carboamination reaction.
Scheme 3
Scheme 3
Carboamination of N-arylsulfonyl-γ- and δ-alkenes. Cu(ND)2 = copper(II) neodecanoate.
Scheme 4
Scheme 4
Carboaminations of γ-alkenyl amides and imides. Cu(EH)2 = copper(II) 2-ethylhexanoate.
Scheme 5
Scheme 5
Possible mechanistic scenarios for C–N bond formation.
Scheme 6
Scheme 6
Proposed enantioselective carboamination catalytic cycle.
Scheme 7
Scheme 7
Synthesis of a calcium-sensing receptor antagonist intermediate.
Scheme 8
Scheme 8
Synthesis of (S)-(+)-tylophorine.
Scheme 9
Scheme 9
Proposed doubly intramolecular alkene diamination mechanism.
Scheme 10
Scheme 10
Conversion to alcohol, aldehyde and amine.
Scheme 11
Scheme 11
Formal synthesis of (+)-monomorine.
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References

    1. Ley SV, Thomas AW. Angew Chem Int Ed Engl. 2003;42:5400–5449. - PubMed
    1. Beletskaya IP, Cheprakov AV. Coord Chem Rev. 2004;248:2337–2364.
    1. Ma D, Cai Q. Acc Chem Res. 2008;41:1450–1460. - PubMed
    1. Evano G, Blanchard N, Toumi M. Chem Rev. 2008;108:3054–3131. - PubMed
    1. Gil MV, Arevalo MJ, Lopez O. Synthesis. 2007:1589–1620.

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