Diastereoselective [3,2]-Stevens and Sommelet-Hauser Rearrangements in the Dihydromethanodibenzoazocine Series

Abstract

Bridged tricyclic dihydroazocines, readily available from α-amino acids were subjected to a series of diastereoselective [3,2]-Stevens and Sommelet-Hauser rearrangements via the corresponding ‘azocinium’ salts. The enantiopure rearrangement products have functionalities that can be used in preparing diversely substituted heterocyclic scaffolds.

sigmatropic rearrangements - nitrogen ylides - tetrahydroisoquinoline

References

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To ascertain the relative stereochemistry of the major and minor products of the [3,2]-Stevens rearrangement products, 2D-NOESY was used in order to look for 1,3-pseudo-diaxial spatial correlations between protons marked as α and β in the case of the minor product 4 and between the proton marked as γ and the methyl group in the case of the major product 3 (Figure [1] ).

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<A NAME="RM05305SS-16">16</A>

CCDC 286054 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

<A NAME="RM05305SS-17">17</A>

CCDC 286055 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.