Highly Regio- and Stereoselective [3+2] Cycloaddition of Carbonyl Ylides with Imines: A Novel Entry to Oxa-Bridged Piperidinone Ring Systems

Abstract

The reaction of α-diazo ketones and N-tosylimines in the presence of a rhodium(II) acetate catalyst led diastereoselectively to the oxa-bridged piperidinone ring systems. The stereochemistry was assigned based on a single-crystal X-ray analysis.

Key words

carbenoids - diazo ketones - imines - piperidinones - rhodium(II) acetate

References

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7

Crystal data for compound 6a: colorless crystals. C₂₃H₂₅NO₄S, M = 411.52, 0.43 × 0.38 × 0.33 mm³, monoclinic, space group Cc, a = 19.5149 (19) Å, b = 14.8813 (14) Å, c = 7.3409 (7) Å, β = 103.786 (2), V = 2070.4 (3) ų, T = 273 (2) K, R ₁ = 0.0349, wR ₂ = 0.0943 on observed data, z = 4, D _calcd = 1.320 gcm^-3, F(000) = 872, Absorption coefficient = 0.186 mm^-1, λ = 0.71073 Å, 3050 reflections were collected on a smart apex ccd single crystal CCD diffractometer, 2906 observed reflections [I≥2σ (I)]. The largest difference peak and hole = 0.199 and -0.162 eÅ^-3, respectively. The structure was solved by direct methods and refined by full-matrix least squares on F ² using SHELXL-97 software.

8

Crystallographic data for 6a have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no CCDC-283331. Copies of the data can be obtained free of charge on application to 12, Union Road, Cambridge CB21EZ, UK. [Fax: [phone]; e-mail: [e-mail]].