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. 2012 Feb 8;134(5):2547-50.
doi: 10.1021/ja212020b. Epub 2012 Jan 27.

Intermolecular Ritter-type C-H amination of unactivated sp3 carbons

Quentin Michaudel  1 , Damien Thevenet, Phil S Baran
Affiliations

Intermolecular Ritter-type C-H amination of unactivated sp3 carbons

Quentin Michaudel et al. J Am Chem Soc. .

Abstract

Intermolecular Ritter-type C-H amination of unactivated sp(3) carbons has been developed. This new reaction proceeds under mild conditions using readily available reagents and an inexpensive source of nitrogen (acetonitrile). A broad scope of substrates can be aminated with this method since many functional groups are tolerated. This reaction also allows for the direct, innate C-H amination of a variety of hydrocarbons such as cyclohexane without the need of prefunctionalization or installation of a directing group.

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Figures

Figure 1
Figure 1
(A) Overview of Csp3–H amination methods (B) Reported synthesis of dihydrooxazinium salt 2 derived from (−)-menthol (1) by Banks et al. and synthesis of hydroxymenthol 3 by Chen et al. (C) Reaction optimization with 2,6-dimethylheptan-4-ol (4) (1.0 equiv, 0.13 mmol).a Number of equivalentsb Yields were determined by 1H NMR with an internal standard.c 16% of recovered starting material 4.
Figure 2
Figure 2
(A) A postulated mechanism for the reaction. (B) Kinetic isotope effect with cyclohexane and cyclohexane d12.
Scheme 1
Scheme 1
Hydrolysis of acetamide products: synthesis of aminomenthol 37
See this image and copyright information in PMC

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