title: Divergent Reactivity of In Situ Generated Metal Azides: Reaction with N,N-Bis(oxy)enamines as a Case Study.
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.
authors.affiliation: Laboratory of Functional Organic Compounds, N. D. Zelinsky Institute of Organic Chemistry, 119991, Leninsky Prospect, 47, Moscow, Russia.
authors.forename: Petr A
authors.identifier: http://orcid.org/0000-0002-5934-4233
authors.initials: PA
authors.lastname: Zhmurov
authors.affiliation: Laboratory of Functional Organic Compounds, N. D. Zelinsky Institute of Organic Chemistry, 119991, Leninsky Prospect, 47, Moscow, Russia.
authors.forename: Yulia A
authors.initials: YA
authors.lastname: Khoroshutina
authors.affiliation: Laboratory of Functional Organic Compounds, N. D. Zelinsky Institute of Organic Chemistry, 119991, Leninsky Prospect, 47, Moscow, Russia.
authors.forename: Roman A
authors.identifier: http://orcid.org/0000-0002-3740-7424
authors.initials: RA
authors.lastname: Novikov
authors.affiliation: Laboratory of Functional Organic Compounds, N. D. Zelinsky Institute of Organic Chemistry, 119991, Leninsky Prospect, 47, Moscow, Russia.
authors.forename: Ivan S
authors.identifier: http://orcid.org/0000-0001-7219-2409
authors.initials: IS
authors.lastname: Golovanov
authors.affiliation: Laboratory of Functional Organic Compounds, N. D. Zelinsky Institute of Organic Chemistry, 119991, Leninsky Prospect, 47, Moscow, Russia.
authors.forename: Alexey Yu
authors.identifier: http://orcid.org/0000-0003-4413-9453
authors.initials: AY
authors.lastname: Sukhorukov
authors.affiliation: Laboratory of Functional Organic Compounds, N. D. Zelinsky Institute of Organic Chemistry, 119991, Leninsky Prospect, 47, Moscow, Russia.
authors.forename: Sema L
authors.initials: SL
authors.lastname: Ioffe
keywords: 1,2-diamines; Lewis acids; metal azides; nitrogen-oxygen bond; organic azides