Chiral phosphinoferrocenyl-calixarenes

Andrii Karpus (1, 2) , Oleksandr Yesypenko (3) , Vyacheslav Boiko (3) , Rinaldo Poli (1, 4) , Jean-Claude Daran (1) , Zoia Voitenko (2) , V. Kalchenko (3) , E. Manoury (1)

1 LCC - Laboratoire de chimie de coordination
2 Taras Shevchenko National University of Kyiv
3 Institute of Organic Chemistry
4 IUF - Institut universitaire de France

The Mitsunobu alkylation of 4-tert-butylcalix[4]arene with (S)-(2-diphenylthiophosphinoferrocenyl)methanol followed by desulfuration of the thiophosphine unit using tris(dimethylamino)phosphine afforded enantiomerically pure calixarene mono- and di(ferrocenylphosphine) ligands in high yields. The calixarene mono(ferrocenylphosphine) ligands exhibited good catalytic activity but low atropoenantioselectivity when used in the asymmetric Suzuki–Miyaura coupling reaction of 1-naphthaleneboronic acid and 1-bromo-2-methylnaphthalene. However, the di(ferrocenylphosphine) ligand displayed both good catalytic activity and enantioselectivity (ee values up to 86 %) when employed in the asymmetric Tsuji–Trost allylic alkylation of 1,3-diphenylprop-2-enyl acetate with dimethyl malonate.

Mots clés: Asymmetric catalysis; Calixarenes; Phosphorus; Cyclopentadienyl ligands; Alkylation

Domaines: Chimie de coordination

Andrii Karpus, Oleksandr Yesypenko, Vyacheslav Boiko, Rinaldo Poli, Jean-Claude Daran, et al.. Chiral phosphinoferrocenyl-calixarenes. European Journal of Organic Chemistry, 2016, 2016 (20), pp.3386-3394. ⟨10.1002/ejoc.201600208⟩. ⟨hal-01929761⟩