title: Lithium choreography: intramolecular arylations of carbamate-stabilised carbanions and their mechanisms probed by in situ IR spectroscopy and DFT calculations.
abstract: Deprotonation of O-allyl, O-propargyl or O-benzyl carbamates in the presence of a lithium counterion leads to carbamate-stabilised organolithium compounds that may be quenched with electrophiles. We now report that when the allylic, propargylic or benzylic carbamate bears an N-aryl substituent, an aryl migration takes place, leading to stereochemical inversion and C-arylation of the carbamate α to oxygen. The aryl migration is an intramolecular S(N) Ar reaction, despite the lack of anion-stabilising aryl substituents. Our in situ IR studies reveal a number of intermediates along the rearrangement pathway, including a "pre-lithiation complex," the deprotonated carbamate, the rearranged anion, and the final arylated carbamate. No evidence was obtained for a dearomatised intermediate during the aryl migration. DFT calculations predict that during the reaction the solvated Li cation moves from the carbanion centre, thus freeing its lone pair for nucleophilic attack on the remote phenyl ring. This charge separation leads to several alternative conformations. The one having Li(+)  bound to the carbamate oxygen gives rise to the lowest-energy transition structure, and also leads to inversion of the configuration. In agreement with the IR studies, the DFT calculations fail to locate a dearomatised intermediate.
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
authors.forename: Anne M
authors.initials: AM
authors.lastname: Fournier
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Nichols
authors.forename: Mark A
authors.initials: MA
authors.lastname: Vincent
authors.forename: Ian H
authors.initials: IH
authors.lastname: Hillier
authors.forename: Jonathan
authors.initials: J
authors.lastname: Clayden
mesh_terms: D002219:Carbamates / Q000737:chemistry*; D003198:Computer Simulation; D008094:Lithium / Q000737:chemistry*; D018020:Lithium Compounds / Q000737:chemistry*; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism
chemical_list: D002219:Carbamates; D018020:Lithium Compounds; D008094:Lithium; D010100:Oxygen