Stereoselectivity and chiral recognition in copper(I) olefin complexes with a chiral diamine

Luigi Cavallo, Maria E. Cucciolito, Alberto De Martino, Federico Giordano, Ida Orabona, Aldo Vitagliano*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

47 Scopus citations

Abstract

Trigonal copper(I) complexes of the chiral bidentate ligand (1S,2S)-N,N′-Bis-(mesitylmethyl)-1,2-diphenyl-1,2-ethanediamine ((S,S)-1) have been prepared with hydrocarbon olefins, as well as with allylic alcohols and ethers. The stereochemistry of the complexes has been investigated by 1H NMR spectroscopy and by combined quantum mechanics and molecular mechanics (QM/MM) computational methods. The coordinated chiral nitrogen atoms can display equal (R, R) or opposite (R, S) configuration, the latter being disfavored if steric hindrance is present above and below the coordination plane. Although the complexes exist as rapidly equilibrated mixtures of stereoisomers, one of these is often dominant, and prochiral olefins are coordinated with high enantioface selection. In addition, the [(S,S)-1]-Cu+ fragment selectively recognizes the R enantiomer of secondary allylic alcohols and ethers, as confirmed by the X-ray crystal structure analysis of the adduct with (R)-1-buten-3-ol. The reasons for the observed selectivities have been elucidated, and lead to some implications which are consistent with the enantioselection observed in catalytic cyclopropanation reactions promoted by copper complexes of the same ligand.

Original languageEnglish (US)
Pages (from-to)1127-1139
Number of pages13
JournalChemistry - A European Journal
Volume6
Issue number7
StatePublished - Apr 3 2000
Externally publishedYes

Keywords

  • Chiral diamine
  • Chirality
  • Copper
  • Enantioselectivity
  • Olefin

ASJC Scopus subject areas

  • Chemistry(all)

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