Stereodivergent Synthesis of Substituted N,O‐Containing Bicyclic Compounds by Sequential Addition of Nucleophiles to N‐Alkoxybicyclolactams

In control! N-alkoxybicyclolactams derived from the ring-rearrangement metathesis of nitroso Diels–Alder cycloadducts were subjected to the successive addition of two nucleophiles to yield substituted piperidine or pyrrolidine precursors with good to excellent stereoselectivity. The relative configuration of the newly formed stereocenter can be controlled by the order of addition of the two nucleophiles.