Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2008 Jul 23;130(29):9220-1.
doi: 10.1021/ja8031955. Epub 2008 Jun 27.

A chiral rhodium carboxamidate catalyst for enantioselective C-H amination

David N Zalatan  1 , J Du Bois
Affiliations

A chiral rhodium carboxamidate catalyst for enantioselective C-H amination

David N Zalatan et al. J Am Chem Soc. .

Abstract

Rh2(S-nap)4, a chiral dirhodium tetracarboxamidate complex, has been developed and shown to be an effective catalyst for the asymmetric, intramolecular C-H amination of sulfamate esters. Enantiomeric excesses range from 60-99% for a collection of disparately substituted 3-arylpropylsulfamates. In addition, Rh2(S-nap)4 is found to promote chemoselective allylic C-H oxidation of unsaturated sulfamates, a property not observed with other dirhodium complexes tested to date.

PubMed Disclaimer

Figures

Figure 1
Figure 1
Optically active amine derivatives through C—H amination.
Figure 2
Figure 2
Evaluating catalyst performance for C—H amination.
Figure 3
Figure 3
Results suggestive of a concerted insertion mechanism.
Table 1
Table 1
Enantioselective Cyclization of Sulfamate Estersa
Table 2
Table 2
Chemoselective Allylic C—H Bond Insertion
See this image and copyright information in PMC

References

    1. Davies HML, Manning JR. Nature. 2008;451:417. - PMC - PubMed
    2. Espino CG, Du Bois J. In: Modern Rhodium-Catalyzed Organic Reactions. Evans PA, editor. Wiley-VHC; Weinheim, Germany: 2005. pp. 379–416.

    1. For a general reference to reactions of diazoalkanes, see: Doyle MP, McKervey MA, Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds: From Cyclopropanes to Ylides. Wiley and Sons, Ltd.; New York: 1997. .

    1. Yamawaki M, Kitagaki S, Anada M, Hashimoto S. Heterocycles. 2006;69:527.
    2. Zhang J, Chan PWH, Che C-M. Tetrahedron Lett. 2005;46:5403.
    3. Fruit C, Müller P. Helv. Chim. Acta. 2004;87:1607.
    4. Liang J-L, Yuan S-X, Chan PWH, Che C-M. Tetrahedron Lett. 2003;44:5917.
    5. Liang JL, Yuan S-X, Huang J-S, Yu W-Y, Che C-M. Angew. Chem., Int. Ed. 2002;41:3465. - PubMed
    6. Yamawaki M, Tsutsui H, Kitagaki S, Anada M, Hashimoto S. Tetrahedron Lett. 2002;43:9561.
    1. Reddy RP, Davies HML. Org. Lett. 2006;8:5016.
    2. Omura K, Murakami M, Uchida T, Irie R, Katsuki T. Chem. Lett. 2003;32:354.
    3. Kohmura Y, Katsuki T. Tetrahedron Lett. 2001;42:3339.

    1. For a diastereoselective intermolecular C—H amination catalyzed by a chiral dirhodium complex, see: Liang C, Collet F, Robert-Peillard F, Müller P, Dodd RH, Dauban P. J. Am. Chem. Soc. 2008;130:343.. Liang C, Robert-Peillard F, Fruit M, Müller P, Dodd RH, Dauban P. Angew. Chem., Int. Ed. 2006;45:4641..

Publication types