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. 2013 Oct 18;52(43):11343-6.
doi: 10.1002/anie.201304238. Epub 2013 Sep 2.

Selective intermolecular amination of C-H bonds at tertiary carbon centers

Jennifer L Roizen  1 , David N Zalatan, J Du Bois
Affiliations

Selective intermolecular amination of C-H bonds at tertiary carbon centers

Jennifer L Roizen et al. Angew Chem Int Ed Engl. .

Abstract

C-H insertion: A method for intermolecular amination of tertiary CH bonds is described that uses limiting amounts of substrate and a convenient phenol-derived nitrogen source. Structure-selectivity and mechanistic studies suggest that steric interaction between the substrate and active oxidant is the principal determinant of product selectivity.

Keywords: C-H insertion; amination; amines; isotope effect; rhodium.

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Figures

Figure 1
Figure 1
Synthesis of tetrasubstituted amine derivatives through intermolecular, Rh-catalyzed tertiary C–H bond amination. TcesNH2 = 2,2,2-trichloroethoxysulfonamide; esp = α,α,α,α′-tetramethyl-1,3-benzenedipropionate.
Figure 2
Figure 2
Influence of sulfonamide on reaction efficiency.
Figure 3
Figure 3
Hot aqueous CH3CN effects amine deprotection.
Figure 4
Figure 4
Enantiospecific insertion into a C–H bond at a tertiary carbon center.
Figure 5
Figure 5
Primary KIE values for intermolecular C–H amination, as determined by 13C NMR integration. Values in parentheses are obtained by HRMS; see the Supporting information for details.
Figure 6
Figure 6
Cis-trans isomerization implicates transient cyclopropyl-car-binyl radical formation.
See this image and copyright information in PMC

References

    1. Special issue:

    2. C–H Functionalization in Organic Synthesis. Chem Soc Rev. 2011;40(4) - PubMed
    3. Yu J-Q, Shi Z, editors. Topics in Current Chemistry. Springer; Berlin: 2010. C–H Activation; pp. 1–384. - PubMed

    1. Recent reviews of carbenoid- and nitrenoid-mediated C–H insertion:

    2. Lebel H. In: Catalyzed Carbon-Heteroatom Bond Formation. Yudin A, editor. Wiley-VCH; Weinheim: 2011. pp. 137–156.
    3. Dequirez G, Pons V, Dauban P. Angew Chem. 2012;124:7498–7510. - PubMed
    4. Angew Chem Int Ed. 2012;51:7384–7395. - PubMed
    5. Gephart RT, III, Warren TH. Organometallics. 2012;31:7728–7752.
    6. Roizen JL, Harvey ME, Du Bois J. Acc Chem Res. 2012;45:911–922. - PMC - PubMed
    7. Stokes BJ, Driver TG. Eur J Org Chem. 2011:4071–4088.
    8. Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem Rev. 2009;109:704–724. - PubMed
    9. Collet F, Dodd RH, Dauban P. Chem Commun. 2009:5061–5074. - PubMed
    10. Diaz-Requejo MM, Perez PJ. Chem Rev. 2008;108:3379–3394. - PubMed

    11. A recent example of intramolecular C–H functionalization:

    12. Hennessy ET, Betley TA. Science. 2013;340:591–595. - PubMed

    1. Selected examples of aminations of C–H bonds at tertiary carbon centers:

    2. Lescot C, Darses B, Collet F, Retailleau P, Dauban P. J Org Chem. 2012;77:7232–7240. - PubMed
    3. Ochiai M, Miyamoto K, Kaneaki T, Hayashi S, Nakanishi W. Science. 2011;332:448–451. - PubMed
    4. Collet F, Lescot C, Liang C, Dauban P. Dalton Trans. 2010;39:10401–10413. - PubMed
    5. Barman DN, Liu P, Houk KN, Nicholas KM. Organometallics. 2010;29:3404–3412.
    6. Baba H, Togo H. Tetrahedron Lett. 2010;51:2063–2066.
    7. Liu Y, Che CM. Chem Eur J. 2010;16:10494–10501. - PubMed
    8. Liang C, Collet F, Robert-Peillard F, Müller P, Dodd RH, Dauban P. J Am Chem Soc. 2008;130:343–350. - PubMed
    9. Huard K, Lebel H. Chem Eur J. 2008;14:6222–6230. - PubMed
    1. Zalatan DN, Du Bois J. J Am Chem Soc. 2009;131:7558–7559. - PMC - PubMed
    2. Fiori KW, Du Bois J. J Am Chem Soc. 2007;129:562–568. - PubMed
    1. Espino CG, Fiori KW, Kim M, Du Bois J. J Am Chem Soc. 2004;126:15378–15379. - PubMed

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