Asymmetric synthesis of P-stereogenic o-hydroxyaryl-phosphine (borane) and phosphine-phosphinite ligands |
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| Affiliation: | 1. Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka 599-8531, Japan;2. Katayama Chemical Industries Co., Ltd., 26-22, 3-Chome, Higasinaniwa-cho, Amagasaki, Hyogo 660-0892, Japan;3. Center for Education and Research in Agricultural Innovation, Faculty of Agriculture, Saga University, 152-1 Shonan-cho, Karatsu, Saga 847-0021, Japan;4. National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1, Higashi, Tsukuba, Ibaraki 305-8565, Japan;1. College of Chemistry, The Key Laboratory of Chemical Biology and Organic Chemistry of Henan Province, Zhengzhou University, Zhengzhou, 450052, PR China;2. Institute of Drug Discovery Technology, Ningbo University, Ningbo, 315211, PR China |
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| Abstract: | The first asymmetric synthesis of P-stereogenic 2-hydroxyarylphosphine ligands is described, using borane complexation methodology. This synthesis is based on the highly stereoselective preparation of bromoarylphosphinite boranes, leading to the 2-hydroxyarylphosphine derivatives, by an intramolecular ortho Fries-like rearrangement mediated in basic conditions. The o-anisyl-2-hydroxynaphthylphenylphosphine borane has been decomplexed in EtOH, affording the P(III)-stereogenic hydroxyarylphosphine ligand with 84% yield. The interest of the hydroxyarylphosphine borane is also demonstrated by the preparation of a new class of phosphine-phosphinite ligands, by trapping the rearrangement products first with chlorodiphenylphosphine, Ph2PCl, then with borane. The corresponding phosphine-phosphinites are obtained and purified as diborane complexes, with the decomplexation of these borane complexes being achieved by heating with dabco, to afford the free hybrid ligands with retention of the configuration at the P-atom (isolated yield up to 53%). |
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