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On the Dichotomic Reactivity of Lithiated Styrene Oxide: A Computational and Multinuclear Magnetic Resonance Investigation
Author(s) -
Capriati Vito,
Florio Saverio,
Perna Filippo Maria,
Salomone Antonio,
Abbotto Alessandro,
Amedjkouh Mohamed,
Nilsson Lill Sten O.
Publication year - 2009
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200900834
Subject(s) - chemistry , reactivity (psychology) , styrene , styrene oxide , deprotonation , diastereomer , resonance (particle physics) , crystallography , density functional theory , computational chemistry , stereochemistry , organic chemistry , ion , polymer , medicine , physics , alternative medicine , pathology , particle physics , copolymer
A multinuclear magnetic resonance investigation, supported by density functional theory calculations, has been synergically used to investigate the configurational stability, reactivity and aggregation states of α‐lithiated styrene oxide in THF at 173 K. NMR studies on α‐lithiated [α,β‐ 13 C 2 ]styrene oxide (also in an enantiomerically enriched form) proved that in THF this oxiranyllithium is mainly present as a solvated monomeric species in equilibrium with a complex mixture of stereoisomeric dimeric aggregates, as well as with bridged and tetrameric aggregates. The fact that some C α Li bonds are partially broken in some stereoisomers reduces their symmetry and complicates the NMR spectra: two diastereoisomers each having a pair of diastereotopic carbon atoms slowly inverting at the lithium atom in absence of tetramethylethylenediamine (TMEDA) have been detected. A ( 13 C, 7 Li)‐HMQC experiment to correlate 7 Li and 13 C resonances of the various aggregates has been performed for the first time. From natural bond analysis, the monomeric aggregate was proven to have a lower carbenoid character with respect to bridged O‐coordinated dimeric aggregates. The employment of suitable experimental conditions in terms of concentration, temperature and the presence or not of TMEDA are crucial to mitigate at the best the “carbene‐like” reactivity of lithiated styrene oxide toward intermolecular CLi insertions, eliminative dimerisation reactions and ring‐opening reactions. A two‐step mechanism for the deprotonation of styrene oxide by s BuLi in THF has been proposed and discussed as well as competitive side reactions.