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. 2015 Nov 25;137(46):14590-14593.
doi: 10.1021/jacs.5b10299. Epub 2015 Nov 13.

Remote Oxidation of Aliphatic C-H Bonds in Nitrogen-Containing Molecules

Jennifer M Howell #  1 , Kaibo Feng #  1 , Joseph R Clark  1 , Louis J Trzepkowski  1 , M Christina White  1
Affiliations

Remote Oxidation of Aliphatic C-H Bonds in Nitrogen-Containing Molecules

Jennifer M Howell et al. J Am Chem Soc. .

Abstract

Nitrogen heterocycles are ubiquitous in natural products and pharmaceuticals. Herein, we disclose a nitrogen complexation strategy that employs a strong Brønsted acid (HBF4) or an azaphilic Lewis acid (BF3) to enable remote, non-directed C(sp(3))-H oxidations of tertiary, secondary, and primary amine- and pyridine-containing molecules with tunable iron catalysts. Imides resist oxidation and promote remote functionalization.

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Figures

Figure 1
Figure 1
Heterocycle Functionalization
Scheme 1
Scheme 1
Amine Deprotection Strategies
Scheme 2
Scheme 2
Late-Stage Functioalization of Nitrogen Containing Moleculesa
See this image and copyright information in PMC

References

    1. Vitaku E, Smith DT, Njardarson JT. J. Med. Chem. 2014;57:10257. - PubMed
    2. White MC. Science. 2012;335:807. - PubMed
    3. Nam W, Lee Y-M, Fukuzumi S. Acc. Chem. Res. 2014;47:1146. - PubMed
    1. Campos KR. Chem. Soc. Rev. 2007;36:1069. - PubMed
    2. Catino AJ, Nichols JM, Nettles BJ, Doyle MP. J. Am. Chem. Soc. 2006;128:5648. - PMC - PubMed
    3. Condie AG, González-Gómez JC, Stephenson CRJ. J. Am. Chem. Soc. 2010;132:1464. - PubMed
    4. Hari DP, König B. Org. Lett. 2011;13:3852. - PubMed
    5. Noble A, MacMillan DWC. J. Am. Chem. Soc. 2014;136:11602. - PMC - PubMed
    6. He J, Hamann LG, Davies HML, Beckwith RE. J. Nat. Commun. 2015;6:5943. - PubMed
    1. McNally A, Haffemayer B, Collins BSL, Gaunt MJ. Nature. 2014;510:129. - PubMed
    2. Chan KSL, Wasa M, Chu L, Laforteza BN, Miura M, Yu J-Q. Nat. Chem. 2014;6:146. - PMC - PubMed
    1. Chen MS, White MC. Science. 2007;318:783. - PubMed
    2. Chen MS, White MC. Science. 2010;327:566. - PubMed
    3. Gormisky PE, White MC. J. Am. Chem. Soc. 2013;135:14052. - PubMed
    1. Anslyn EV, Dougherty DA. Modern Physical Organic Chemistry; University Science Books; California: 2006. pp. 15–16.
    2. Staubitz A, Robertson APM, Sloan ME, Manners I. Chem. Rev. 2010;110:4023. - PubMed

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