Heterocycles containing a nitrogen-oxygen bond, i.e. cyclic hydroxylamines, are useful intermediates for alkaloid synthesis. These heterocycles have traditionally been made by cycloaddition reactions. For about 15 years, we have been exploring alternative routes to these heterocycles, using transition metal catalysis to facilitate ring formation, to obtain alternative stereo- and regiochemical outcomes. The resulting heterocycles have been employed in syntheses of a range of alkaloids inlcuding both sedum and nuphar alkaloids. We have recently shown that this strategy can be broadened by the use of iminium chemistry, resulting in a synthesis of negamycin employing an unusual electrostatic effect to ensure complete stereochemical control.

New routes to N,O-heterocycles for alkaloid synthesis

251st National Meeting (2016)

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