om950922o_si_001.pdf (1.24 MB)
1,3-Dipolar Cycloaddition to the FeNC Fragment. 17. Diastereoselectivity with C2- and non-C2-Symmetric Chirally N-Substituted α-Diimine Ligands, R*NC(H)C(R‘)NR* and C5H4N-2-C(R‘)NR*, with Dimethyl Acetylenedicarboxylate (DMAD) and Methyl Propiolate (MP). Decomplexation of the Pyrrolinone Ligand of Fe(CO)3(pyrrolinone) Complexes
journal contribution
posted on 1996-04-16, 00:00 authored by Nantko Feiken, Pieter Schreuder, Ron Siebenlist, Hans-Werner Frühauf, Kees Vrieze, Huub Kooijman, Nora Veldman, Anthony L. Spek, Jan Fraanje, Kees GoubitzThe 1,3-dipolar cycloaddition reaction of
Fe[R*-DAB(H;H)](CO)3 (6k;
R*-DAB(H;H) =
R*NC(H)C(H)NR*) with dimethyl
acetylenedicarboxylate (DMAD), in which the R*-DAB(H;H) ligand is C2-symmetric and is
chirally N-substituted, gives the two expected
diastereomers with low diastereoselectivity, due to a small difference
in the rate constants
of the two reactive CN groups in 6k exposing their
re and si faces, respectively. The
1,3-dipolar cycloaddition reaction of
Fe(α-diimine)(CO)3 (1,
6m) with DMAD and methyl
propiolate (MP), in which a non-C2-symmetric
α-diimine ligand (R*-DAB(H;Me) and Py-2-C(R‘)NR* (R*,R‘-PyCa) is chirally N-substituted, gives the two
expected diastereomers
with medium to high diastereoselectivity. The diastereoselectivity
with the non-C2-symmetric
α-diimine ligands, which have only one reactive imino group, depends
on the size of the
chiral group R*, the distance of the chiral group to the reacting
centers, and the type of
dipolarophile. The two starting complexes (1 and
6m) exist in solution in the form of two
rapidly interconverting diastereomeric conformers I and II. In
contrast to the C2-symmetric
case, the free energies of activation for the two different conformers
and their respective
concentrations may be quite different here. The
diastereoselectivities could not be influenced
by variation of temperature, solvent, or the additional ligand.
Kinetic resolution by a
cycloreversion reaction could be excluded by the use of a chiral
additional ligand and an
achiral α-diimine ligand (i-Pr, H-PyCa, or
i-Pr-DAB(H; H)). X-ray crystal structures
have
been determined from the respective diastereomeric mixtures of the
pyrrolinone complex
5cks and the [2.2.2] bicyclic product 7aks.
The structures of the [2.2.2] bicyclic product
4aks and of the free pyrrolinone ligand 8als have
been determined using diastereomerically
pure products. The 5-(2-pyridyl)pyrrolin-2-one ligands
8 are decomplexed from their
precursors 5 by Me3NO, air oxidation,
exchange by CO, and oxidative reactions with
dihalogens or H2O2.