Homochiral and heterochiral dimers of the methylzinc alkoxide formed from dimethylzinc and enantiomeric 3-exo-(dimethylamino)isoborneol - Origin of the distinct differences in solution-phase behavior and crystal structures

Masato Kitamura, Masashi Yamakawa, Hiromasa Oka, Seiji Suga, Ryoji Noyori

Research output: Contribution to journalArticlepeer-review

83 Citations (Scopus)

Abstract

Dimethylzinc reacts with (2S)-or (2R)-3-exo-(dimethylamino)isoborneol [(2S)- or (2R)-DAIB] to eliminate methane and produce a tricoordinate methylzinc aminoalkoxide, which forms a dimeric structure. The homochiral dimerization of the enantiomeric compound leads to the chiral, (S,S) or (R,R) dinuclear Zn complex, while the heterochiral interaction forms the meso (S,R) dinuclear compound. In both solution and crystalline state, the heterochiral dimer is more stable than the homochiral dimer. This stability difference in solution is the origin of the chirality amplification observed in the amino alcohol promoted asymmetric addition of dimethylzinc to benzaldehyde. In toluene, the homochiral dimer dissociates more readily into the monomer than the heterochiral isomer and also undergoes dissociation of the N-Zn dative bond making the two N-methyl groups equivalent. The differences in solution behavior between the diastereomers can be understood by comparing their crystal structures. X-ray analysis indicates that the labile Zn-O and Zn-N bonds in the (S,S) dimer are longer than those in the (S,R) isomer. Skeletal congestion caused by the polycyclic framework is the prime factor determining the properties of the dinuclear Zn complexes, with both steric and electronic factors governing their geometries. The distances between the C-2 proton and N-CH3 of the other DAIB moiety in the homochiral dimer are close to the sum of the van der Waals radii. A significant nuclear Overhauser effect is seen between these protons in the homochiral dimer. The tetrahedral Zn atoms in the dinuclear complexes are linked covalently to the methyl group, to two oxygen atoms through covalent/electrostatic hybrid bonds, and to the dimethylamino group through electrostatic interaction. The repulsive interaction of the 1,3-synoriented Zn-CH3 bonds significantly contributes to the lower stability of the homochiral dimeric complex. The N-Zn interaction in the homochiral dimer is labile, owing to the increase in the electrostatic interaction between the Zn atom and the neighboring oxygen atoms. This view is supported by the ab initio molecular orbital calculations of the model systems.

Original languageEnglish
Pages (from-to)1173-1181
Number of pages9
JournalChemistry - A European Journal
Volume2
Issue number9
DOIs
Publication statusPublished - Dec 1 1996
Externally publishedYes

Keywords

  • Ab initio calculations
  • Asymmetric alkylations
  • Catalysis
  • Structure elucidation
  • Zinc complexes

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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