TY - JOUR A1 - Imrich, Michael R. A1 - Kraft, Jochen A1 - Maichle-Mössmer, Cäcilia A1 - Ziegler, Thomas T1 - D-Fructose-based spiro-fused PHOX ligands: synthesis and application in enantioselective allylic alkylation JF - Beilstein Journal of Organic Chemistry PY - 2018/// VL - 14 SP - 2082 EP - 2089 SN - 1860-5397 DO - 10.3762/bjoc.14.182 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.14.182 KW - Fürst–Plattner rule KW - oxazoline KW - Ritter reaction KW - Tsuji–Trost reaction KW - Ullmann coupling N2 - Phosphinooxazoline (PHOX) ligands are an important class of ligands in asymmetric catalysis. We synthesized ten novel D-fructose-derived spiro-fused PHOX ligands with different steric and electronic demand. The application of two of them was tested in asymmetric allylic alkylation. The ligands are prepared in two steps from readily available 1,2-O-isopropylidene protected β-D-fructopyranoses by the BF3·OEt2-promoted Ritter reaction with 2-bromobenzonitrile to construct the oxazoline moiety followed by Ullmann coupling of the resulting aryl bromides with diphenylphosphine. Both steps proceeded mostly in good to high yields (57–86% for the Ritter reaction and 35–89% for the Ullmann coupling). The Ritter reaction gave two anomers, which could be separated by column chromatography. The prepared ligands showed promising results (er of up to 84:16) in Tsuji–Trost reactions with diphenylallyl acetate as model substrate. ER -