Abstract: Metal azides generated in situ by ion exchange exhibit divergent reactivity in reaction with cyclic N-alkoxy,N-siloxy-enamines. Depending on the nature of metal and the [M]/N3− ratio, addition of the azide ion to the C,C-double bond proceeds with regioselective cleavage of either exo- or endo-cyclic N−O bond leading to cyclic or open-chain α-azidooxime derivatives, respectively. Mechanistic studies in combination with solvent state FTIR spectroscopy and DFT calculations revealed that covalently bound metal azides (Co, Cu, Zn) transfer N3− anion to the C,C-double bond through a Lewis acid-assisted SN′ substitution of trialkylsilyloxy-group. More ionic metal azides (N1, Mg, Al, Sc, Ni, Yb) tend to react by initial nucleophilic attack of N3− anion on the silicon atom generating conjugated nitrosoalkenes. α-Azidooxime derivatives prepared by using the designed protocols were stereoselectively reduced to valuable 1,2-diaminoalcohols bearing up to four contiguous stereogenic centers. By reducing the α-azidooxime fragment in a stepwise manner site-selective protection and reductive amination of each of the emerging primary amino groups was achieved.

Cite: Zhmurov P.A. , Khoroshutina Y.A. , Novikov R.A. , Golovanov I.S. , Sukhorukov A.Y. , Ioffe S.L.
Divergent Reactivity of In Situ Generated Metal Azides: Reaction withN,N-Bis(oxy)enamines as a Case Study
Chemistry: A European Journal. 2017. V.23. N19. P.4570-4578. DOI: 10.1002/chem.201605390 WOS Scopus OpenAlex

Identifiers:

Web of science:	WOS:000399326500009
Scopus:	2-s2.0-85012050440
OpenAlex:	W2564764166

Citing:

DB	Citing
OpenAlex	25
Scopus	26
Web of science	25

Altmetrics: