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Synthesis of 1,3-Difunctionalized Amine Derivatives through Selective C-H Bond Oxidation

Christine G. Espino, Paul M. Wehn, Jessica Chow and Justin Du Bois

*Department of Chemistry, Stanford University Stanford, California 94305, Email: jduboisstanford.edu

C. G. Espino, P. M. Wehn, J. Chow, J. Du Bois, J. Am. Chem. Soc., 2001, 123, 6935-6936.

DOI: 10.1021/ja011033x


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Abstract

Intramolecular C-H amination using commercial Rh-catalysts, PhI(OAc)2, and MgO offers a practical solution for the controlled oxidation of saturated C-H bonds. Reactions of sulfamates with 2 mol % Rh2(OAc)4, PhI(OAc)2, and MgO yield selectively six-membered ring oxathiazinanes. These heterocycles can serve as precursors for 1,3-amino alcohols, β-amino acids, and numerous other amine derivatives.

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representative oxathiazinane ring-opening reactions



Oxathiazinane Preparation - General Procedure

To a solution of sulfamate ester (1.25 mmol) in 8 ml of CH2Cl2 were added sequentially MgO (116 mg, 3.0 mmol, 2.3 eq.), PhI(OAc)2 (443 mg, 1.4 mmol, 1.1 eq.) and 25 Ámol (0.02 eq.) of Rh2(OAc)4 or Rh2(oct)4 as indicated. The suspension was stirred vigorously and heated at 40░C until complete consumption of starting material was indicated by thin layer chromatography (1-2 h), The reaction was cooled to 25░C, diluted with 20 ml of CH2Cl2, and filtered through a pad of Celite (30 x 20 mm). The filter cake was rinsed with 2 x 15 ml of CH2Cl2 and the combined filtrates were evaporated under reduced pressure. The residue was purified by chromatography on siliga gel to afford the oxathiazinane product.


Key Words

1,3-amino alcohols, Phenyliodonium Diacetate


ID: J48-Y2001