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- Title
One-Handed Single Helicates of Dinickel(II) Benzenehexapyrrolea, α,ω -diimine with an Amine Chiral Source.
- Authors
Eerdun, Chaolu; Hisanaga, Satoshi; Setsune, Jun‐ichiro
- Abstract
Benzenehexapyrrole-α,ω-dialdehyde, composed of a pair of formyltripyrrole units with a 1,3-phenylene linker, was metallated to give dinuclear single-stranded helicates. X-ray studies of the bis-nickel(II) complex showed a helical C2 form with a pair of helical-metal coordination planes of a 3N+O donor set. The terminal aldehyde was readily converted into the imine by optically active amines, whereby helix-sense bias was induced. Bis-nickel(II) and bis-palladium( II) complexes of the benzenehexapyrrole-α,ω-diimines were studied to show that an enantiomer pair of the helical C2 form are interchanged by slow flipping of each coordination plane and fast rotation around the C(benzene)-C(pyrrole) bond. The helical screw in the bis-nickel(II) complexes was biased to one side in more than 95% diastereoselectivity, which was achieved by using a variety of optically active amines, such as (R)-1-cyclohexylethylamine, (S)-1- phenylethylamine, l-Phe(OEt) (Phe=phenylalanine), and (R)- valinol. The nickel complexes showed much better diastereoselectivity than the corresponding palladium complexes.
- Subjects
ALDEHYDES; PHENYLENE compounds; PALLADIUM; PHENETHYLAMINES; RADIOSCOPIC diagnosis
- Publication
Chemistry - A European Journal, 2015, Vol 21, Issue 1, p239
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.201404782