title: 2-Lithio-3,3-dimethyl-2-oxazolinyloxirane: carbanion or azaenolate? Structure, configurational stability, and stereodynamics in solution.
abstract: Chemical studies have shown that, in ethereal solvents, oxiranyllithium Li-1 is configurationally unstable either on the macroscopic (Hoffmann's text) or microscopic time scale at low temperature (175 K). An optically pure sample of oxazolinyloxirane 1, once deprotonated, racemized within 1 min at -130 degrees C in THF/Et(2)O (3:2) (t(1/2) = 6.05 s); the application of the Eyring equation suggested a barrier to inversion for Li-1 of 8.8 kcal/mol at -130 degrees C. Despite this, Li-1 exhibited an unusual thermal stability undergoing a successfully deuterium incorporation (>98%) also at 25 degrees C with a little decomposition. The structure, configurational stability, and stereodynamics in solution of alpha-lithiated oxazolinyloxirane Li-1 have been also synergically investigated by means of in situ IR and NMR spectroscopy. IR spectroscopic studies showed that lithiation of 1 is complete at -98 degrees C within 1 min and is accompanied by a decrease of the CN wavenumber by only 60 cm(-1), so supporting the idea that the structure of Li-1 may be more similar to that of an "organolithium" rather than an "azaenolate". In addition to this, multinuclear magnetic resonance studies suggested that at least in a range of concentration of 0.08-0.3 M, Li-1 mainly exists in THF as a monomeric eta(3)-aza-allyl coordinated species rapidly equilibrating, on the NMR time scale, with a complex mixture of diastereomeric oxazoline-bridged dimeric species variously intraaggregated. An exchange mechanism by which monomers would interchange their Li atoms via one of the above dimeric species and which may be responsible for the fast racemization Li-1 undergoes as soon as is generated has been proposed.
authors.affiliation: Dipartimento Farmaco-Chimico, Università di Bari, Consorzio Interuniversitario Nazionale Metodologie e Processi Innovativi di Sintesi C.I.N.M.P.I.S., Via E. Orabona 4, I-70125 Bari, Italy. capriati@farmchim.uniba.it
authors.forename: Vito
authors.initials: V
authors.lastname: Capriati
authors.forename: Saverio
authors.initials: S
authors.lastname: Florio
authors.forename: Renzo
authors.initials: R
authors.lastname: Luisi
authors.forename: Filippo Maria
authors.initials: FM
authors.lastname: Perna
authors.forename: Agnese
authors.initials: A
authors.lastname: Spina
mesh_terms: D000838:Anions / Q000737:chemistry; D001372:Aza Compounds / Q000737:chemistry*; D004987:Ethers; D005027:Ethylene Oxide / Q000031:analogs & derivatives* / Q000737:chemistry; D008094:Lithium / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D012997:Solvents; D013055:Spectrophotometry, Infrared; D013237:Stereoisomerism; D013696:Temperature
chemical_list: C543791:2-lithio-3,3-dimethyl-2-oxazolinyloxirane; D000838:Anions; D001372:Aza Compounds; D004987:Ethers; D009942:Organometallic Compounds; D012997:Solvents; D008094:Lithium; D005027:Ethylene Oxide