title: Chemo-, regio-, and stereoselective silver-catalyzed aziridination of dienes: scope, mechanistic studies, and ring-opening reactions.
abstract: Silver complexes bearing trispyrazolylborate ligands (Tp(x)) catalyze the aziridination of 2,4-diene-1-ols in a chemo-, regio-, and stereoselective manner to give vinylaziridines in high yields by means of the metal-mediated transfer of NTs (Ts = p-toluensulfonyl) units from PhI═NTs. The preferential aziridination occurs at the double bond neighboring to the hydroxyl end in ca. 9:1 ratios that assessed a very high degree of regioselectivity. The reaction with the silver-based catalysts proceeds in a stereospecific manner, i.e., the initial configuration of the C═C bond is maintained in the aziridine product (cis or trans). The degree of regioselectivity was explained with the aid of DFT studies, where the directing effect of the OH group of 2,4-diene-1-ols plays a key role. Effective strategies for ring-opening of the new aziridines, deprotection of the Ts group, and subsequent formation of β-amino alcohols have also been developed.
authors.affiliation: Departament de Química Analítica i Química Orgànica, Facultat de Química, Universitat Rovira i Virgili , C/Marcel·lí Domingo s/n, 43007 Tarragona, Spain.
authors.forename: Josep
authors.initials: J
authors.lastname: Llaveria
authors.forename: Álvaro
authors.initials: Á
authors.lastname: Beltrán
authors.forename: W M C
authors.initials: WM
authors.lastname: Sameera
authors.forename: Abel
authors.initials: A
authors.lastname: Locati
authors.forename: M Mar
authors.initials: MM
authors.lastname: Díaz-Requejo
authors.forename: M Isabel
authors.initials: MI
authors.lastname: Matheu
authors.forename: Sergio
authors.initials: S
authors.lastname: Castillón
authors.forename: Feliu
authors.initials: F
authors.lastname: Maseras
authors.forename: Pedro J
authors.initials: PJ
authors.lastname: Pérez
mesh_terms: D000466:Alkadienes / Q000737:chemistry*; D001388:Aziridines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D000466:Alkadienes; D001388:Aziridines; D009942:Organometallic Compounds; D012834:Silver