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
. 2007 Jul 2;63(27):6075-6087.
doi: 10.1016/j.tet.2007.03.071.

Development and application of versatile bis-hydroxamic acids for catalytic asymmetric oxidation

Allan U Barlan  1 , Wei Zhang, Hisashi Yamamoto
Affiliations

Development and application of versatile bis-hydroxamic acids for catalytic asymmetric oxidation

Allan U Barlan et al. Tetrahedron. .

Abstract

In this article, we describe the development and preliminary results of our new designed C(2)-symmetric bis-hydroxamic acid (BHA) ligands and the application of the new ligands for vanadium-catalyzed asymmetric epoxidation of allylic alcohols as well as homoallylic alcohols. From this success we demonstrate the versatile nature of BHA in the molybdenum catalyzed asymmetric oxidation of unfunctionalized olefins and sulfides.

PubMed Disclaimer

Figures

Scheme 1
Scheme 1
BHA metal complexes asymmetric oxidation reactions.
Scheme 2
Scheme 2
Hydroxamic acid ligands.
Scheme 3
Scheme 3
Preparation of BHA ligands.
Scheme 4
Scheme 4
Kinetic resolution of allylic alcohol.
Scheme 5
Scheme 5
Kinetic resolution of homoallylic alcohols.
Scheme 6
Scheme 6
Scheme 7
Scheme 7
Regio- and enantioselective oxidation of squalene.
Scheme 8
Scheme 8
Proposed transition state for Mo-BHA.
See this image and copyright information in PMC

References

    1. For recent reviews, see Katsuki T. In: Comprehensive Asymmetric Catalysis. Jacobsen EN, Pfaltz A, Yamamoto H, editors. Vol. 2. Berlin: Springer; 1999. p. 621. Katsuki T, Ojima I. Org. React. 1996;48:1. Keith JM, Larrow JF, Jacobsen EN. Adv. Synth. Catal. 2001;343:5. Adam W, Saha-Möller CR, Ganeshpure PA. Chem. Rev. 2001;101:3499. Adam W, Malisch W, Roschmann KJ, Möller CR, Schenk WA. J. Organomet. Chem. 2002;661:3. Lattanzi A, Scettri A. J. Organomet. Chem. 2006;691:2072. Shi Y. Acc. Chem. Res. 2004;37:488. Shi Y, Frohn M. Synthesis. 2000;14:1979.

    1. Katsuki T, Sharpless KB. J. Am. Chem. Soc. 1980;102:5974.
    2. Rossiter BE, Sharpless KB. J. Org. Chem. 1984;49:3707.
    3. Gao Y, Hanson RM, Klunder JM, Ko SY, Masamune H, Sharpless KB. J. Am. Chem. Soc. 1987;109:5765.

    1. For recent reports on chiral vanadium catalyst for epoxidation, see Bryliakov KP, Talsi EP. Kinetics and Catalysis (Translation of Kinetika i Kataliz) 2003;44:334. Bolm C, Kuhn T. Synlett. 2000:899. Traber B, Jung YG, Park TK, Hong JI. Bull. Korean Chem. Soc. 2001;22:547. Wu HL, Uang BJ. Tetrahedron: Asymmetry. 2002;13:2625. Bourhani Z, Malkov AV. Chem. Commun. 2005:4592. Lattanzi A, Piccirillo S, Scettri A. Eur. J. Org. Chem. 2005:1669.

    1. For recent reports on achiral metal catalyst and chiral oxidant see Adam W, Alsters PL, Neumann R, Saha-Möller CR, Seebach D, Beck AK, Zhang R. J. Org. Chem. 2003;68:8222. Adam W, Beck AK, Pichota A, Saha-Möller CR, Seebach D, Vogl N, Zhang R. Tetrahedron: Asymmetry. 2003;14:1355. Adam W, Alsters PL, Neumann R, Saha-Möller CR, Seebach D, Zhang R. Org. Lett. 2003;5:725.

    1. For recent reviews on vanadium see, Hirao T. Chem. Rev. 1997;97:2707. Bolm C. Coordination Chemistry Reviews. 2003;237:245.

LinkOut - more resources