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. 2015 Oct 14;137(40):12796-9.
doi: 10.1021/jacs.5b09099. Epub 2015 Oct 6.

Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines

Melissa Lee  1 , Melanie S Sanford  1
Affiliations

Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines

Melissa Lee et al. J Am Chem Soc. .

Abstract

This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.

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Figures

Figure 1
Figure 1
Formation and Decay of Intermediate A in the Pt-Catalyzed C–H Oxidation of Dibutylamine
Scheme 1
Scheme 1
Competition Between N-Propyl and N-Butylpyrrolidine
Scheme 2
Scheme 2
Comparison of Selectivity of (a) Ir-Catalyzed C–H Borylation versus (b) Pt-Catalyzed C–H Oxygenation of Diethylbutylamine
Scheme 3
Scheme 3
Pt-Catalyzed C(sp3)–H Chlorination and Subsequent Functionalization of 20 and 24
See this image and copyright information in PMC

References

    1. Crabtree RH. Chem. Rev. 1985;85:245.
    2. Shilov AE, Shul’pin GB. Chem. Rev. 1997;97:2879. - PubMed
    3. Crabtree RH. J. Chem. Soc.; Dalton Trans. 2001:2437.
    4. Labinger JA, Bercaw JE. Nature. 2002;417:507. - PubMed
    5. Pérez PJ. Alkane C-H Activation by Single-Site Metal Catalysis. In: Pérez PJ, editor. Catalysis by Metal Complexes. Vol. 38. Dordrecht, The Netherlands: Springer; 2012.
    1. Hartwig JF. Chem. Soc. Rev. 2011;40:1992. - PubMed
    1. Davies HML, Manning JR. Nature. 2008;451:417. - PMC - PubMed
    2. Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010;110:704. - PubMed
    3. Nam W. Acc. Chem. Res. 2007;40:522. - PubMed
    4. White MC. Science. 2012;335:807. - PubMed
    1. Lersch M, Tilset M. Chem. Rev. 2005;105:2471. - PubMed
    2. Stahl SS, Labinger JA, Bercaw JE. Angew. Chem. Int. Ed. 1998;37:2180. - PubMed
    3. Shilov AE, Shteinman AA. Coord. Chem. Rev. 1977;24:97.
    1. Gol’dshlger NF, Tyabin MB, Shilov AE, Shteinman AA. Zh. Fiz. Khim. 1969;43:2174.
    2. Gol’dshlger NF, Eskova VV, Shilov AE, Shteinman AA. Zh. Fiz. Khim. 1972;46:1353.

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