Towards the limit of atropochiral stability: H-MIOP, an N-heterocyclic carbene precursor and cationic analogue of the H-MOP ligand. - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2011

Towards the limit of atropochiral stability: H-MIOP, an N-heterocyclic carbene precursor and cationic analogue of the H-MOP ligand.

Ibrahim Abdellah
Yves Canac
Christine Lepetit
Rémi Chauvin

Résumé

The configurational stability of biaryl motifs is addressed for the 1-naphthyl-N-benzimidazolyl motif substituted by a single diphenylphosphinyl group at the 2-position. The atropoenantiomers of the N-methylated cation H-MIOP, a less sterically locked analogue of the neutral H-MOP ligand, were resolved by enantiospecific cleavage of the N(2)C-P bond of the resolved enantiomers of BIMIONAP. The latter were obtained by enantiospecific N-methylation of the previously resolved enantiomers of neutral BIMINAP. PdCl(2) complexes of the P,C-chelating N-heterocyclic carbene (NHC)-phosphine ligands derived from (R)- and (S)-H-MIOP were prepared by two enantiospecific routes: by N(2)C-P bond cleavage from the (R)- and (S)-BIMIONAP-PdCl(2) complexes, or by simultaneous coordination of the P and C atoms of the in situ generated free NHC-phosphine. The enantiomerization pathways of H-MOP, H-MIOP, and corresponding NHC-phosphine have been investigated at the B3PW91/6-31G(d,p) level of theory. The calculated enantiomerization barriers of H-MOP and H-MIOP in acetonitrile are equal to 176.0 and 146.4 kJ mol(-1), respectively, and are mainly determined by the distortion of the naphthalene and/or benzimidazole motifs in the transition state. Beyond the stability of their optical rotation at room temperature, the respective calculated Oki's racemization temperatures of 334 and 225 °C allowed us to consider both ligands as configurationally stable.

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Autre

Dates et versions

hal-00837998 , version 1 (24-06-2013)

Identifiants

Citer

Ibrahim Abdellah, Martial Boggio-Pasqua, Yves Canac, Christine Lepetit, Carine Guyard-Duhayon, et al.. Towards the limit of atropochiral stability: H-MIOP, an N-heterocyclic carbene precursor and cationic analogue of the H-MOP ligand.. Chemistry - A European Journal, 2011, 17 (18), pp.5110-5. ⟨10.1002/chem.201100205⟩. ⟨hal-00837998⟩
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