This review focuses on the role of the nitrogen-oxygen bond as a structural cornerstone for the construction of complex natural products. This bond may play several roles such as a functional protecting group or an activating group in carbonyl chemistry. Compounds containing a N-O bond are generally prepared by cycloaddition of nitroso derivatives, nitrones or nitriles oxides. The first two reactions have been used in the synthesis of a N-O bond containing natural product, pyrinodemin A, or for the synthesis of hydroxylated piperidine alkaloids after N-O bond cleavage. © 2020 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim