144913-06-4Relevant articles and documents
Chiral aminoalcohols and squaric acid amides as ligands for asymmetric borane reduction of ketones: Insight to in situ formed catalytic system by DOSY and multinuclear NMR experiments
Dobrikov, Georgi M.,Nikolova, Yana,Petkova, Zhanina,Shestakova, Pavletta
supporting information, (2021/11/27)
A series of squaric acid amides (synthesized in 66–99% isolated yields) and a set of chiral aminoalcohols were comparatively studied as ligands in a model reaction of reduction of α-chloroacetophenone with BH3?SMe2. In all cases, the aminoalcohols demonstrated better efficiency (up to 94% ee), while only poor asymmetric induction was achieved with the corresponding squaramides. A mechanistic insight on the in situ formation and stability at room temperature of intermediates generated from ligands and borane as possible precursors of the oxazaborolidine-based catalytic system has been obtained by1H DOSY and multinuclear 1D and 2D (1H,10/11B,13C,15N) NMR spectroscopy of equimolar mixtures of borane and selected ligands. These results contribute to better understanding the complexity of the processes occurring in the reaction mixture prior to the possible oxazaborolidine formation, which play a crucial role on the degree of enantioselectivity achieved in the borane reduction of α-chloroacetophenone.
Modularly evolved 2-aminodmap/squaramides as highly active bifunctional organocatalysts in Michael addition
I?k, Murat,Unver, M. Yagiz,Tanyeli, Cihangir
, p. 828 - 835 (2015/03/03)
We report a new family of chiral bifunctional acid/base type organocatalysts, 2-aminoDMAP/Squaramides, which are proved to be highly active (1 mol % cat. loading) promoters in conjugate addition of dibenzoylmethane to various trans-β-nitroalkenes. Steric demand of the catalysts was clearly seen by a set-by-set modulation of the squaramide unit through electronic and steric factors. The synergistic cooperation of 2-aminoDMAP "uperbase" and sterically encumbered squaramide (H-bond donor) enabled complete conversion of a range of reactants into corresponding Michael adducts in a couple of hours with exquisite selectivities (up to 98% ee).
Tether-free immobilized bifunctional squaramide organocatalysts for batch and flow reactions
Kardos, Gyoergy,Soos, Tibor
supporting information, p. 4490 - 4494 (2013/07/26)
This paper describes the preparation of highly efficient, easily accessible, and robust immobilized bifunctional organocatalysts. There was no need to employ any tether to secure high enantio- and diastereoselectivities in various Michael addition reactions. The synthetically useful Michael adducts were obtained within reasonable reaction times with the advantage of easy product isolation and the possibility of automation by using a flow chemistry apparatus. Easily accessible, robust, and cheap immobilized organocatalysts are developed and used to prepare Michael adducts in excellent yields with excellent enantioselectivities, even on the gram scale. Copyright