2-Dihydromethylpiperazinediium-M(II) (M(II) = Cu(II), Fe(II), Co(II), Zn(II)) double sulfates and their catalytic activity in diastereoselective nitroaldol (Henry) reaction.
A series of double dihydromethylpiperazinediium metallic sulfates 1-7 [H(2)mpz]M(II)(SO(4))(2)·nH(2)O (mpz = 2-methylpiperazine, C(5)H(12)N(2)) are prepared by slow evaporation using a racemic (R/S)-mpz (for 1, 2) or enantiopure R-mpz (for 3), S-mpz (for 4-7) and sulfates of Cu(II) (for 5), Fe(II) (for 1, 4), Co(II) (for 7) and Zn(II) (for 2, 3, 6), and characterized by infrared spectroscopy, elemental analysis and single crystal X-ray diffraction. The [M(II)(H(2)O)(6)](2+), [(R/S)-H(2)mpz](2+), [(R)-H(2)mpz](2+) or [(S)-H(2)mpz](2+) cations and 2SO(4)(2-) anions are linked together via two types of hydrogen bonds, Ow-Hw···O and N-H···O, leading to supramolecular arrangements. The use of the racemic 2-mpz provides alternatives in crystallization: a centrosymmetric structure where the enantiomers are related by an appropriate crystallographic symmetry operation or one where the enantiomers occupy the same crystallographic position, generating disorder. Compounds 1-7 act as diastereoselective catalysts for the nitroaldol (Henry) reaction. The diastereoselectivity can be regulated from exclusive threo to exclusive erythro isomer preparation with typical yields of 50-99%, depending on the catalyst and the substrate used.
Laboratoire de l'Etat Solide, Département de Chimie, Université de Sfax, BP 1171, 3000 Sfax, Tunisie. houcine_naili@yahoo.com
Houcine
H
Naïli
Fadhel
F
Hajlaoui
Tahar
T
Mhiri
Tatiana C O
TC
Mac Leod
Maximilian N
MN
Kopylovich
Kamran T
KT
Mahmudov
Armando J L
AJ
Pombeiro