二碘化钐介导的自由基偶联反应.ppt

Introduction  Ketyl Radical-Alkene/Alkyne/Arene Cross-Coupling Pinacol-Type Couplings Cross-Coupling of Imines and Equivalents Grignard and Barbier Reactions Reformatsky Reactions Our Project α-halo esters; α-halo amides; α-halo ketones; α-halo nitriles. * Cross-Coupling Reactions Using Samarium(II) Iodide 指导老师：王 震 报告人：王晓东 2016年2月22日 School of Pharmacy Lanzhou University * 1977, Henri Boris Kagan1,2 introduced Samarium(II) Iodide to organic synthesis; (1) high reductive potential [E0(aq)(Sm3＋/Sm2＋)＝－1.55 V], single-electron transfer reagents; (2) good solubility in organic solvents; (3) powerful chemoseletivity and stereoselectivity. 1.Kagan H. B. et al. Nouv. J. Chim. 1977, 1, 5. 2.Kagan H. B. et al. J.A.C.S. 1980, 102, 2693. reductive couplings to make C?C bonds reductive manipulations of functional groups 2.Cross-Coupling via Ionic Intermediates 1.Cross-Coupling via Radical Intermediates Ketyl Radical-Alkene/Alkyne/Arene Cross-Coupling Pinacol-Type Couplings Cross-Coupling of Imines and Equivalents Grignard and Barbier Reactions Reformatsky Reactions Aldol Reactions Cross-Coupling of Ketyl Radicals with Alkenes Cross-Coupling of Ketyl Radicals with Alkynes Cross-Coupling of Ketyl Radicals with Allenes Cross-Coupling of Ketyl Radicals with Arenes Cross-Coupling of Ketyl Radicals with Alkenes α,β-Unsaturated Esters α,β-Unsaturated Amides Enones α,β-Unsaturated Esters David J. P. et al.O.L.2003,5,4811 F. Matsuda et al. J.O.C. 2004, 69, 8956 α,β-Unsaturated Amides David J. P. et al. O.L. 2008, 10, 4291 Enones D.-S. Hsu et al. Tetrahedron Letters 2012, 53, 2185 D. Ma. et al. A.C.I.E. 2010, 49, 5887 Cross-Coupling of Ketyl Radicals with Alkynes Doo W.?K. et al. Synlett 2001, 627 A. P. Rauter et al. Chem. Eur. J. 2008, 14, 10066 Cross-Coupling of Ketyl Radicals with Allenes H.-U.Reissig et al. OL. 2003, 5,1463 Cross-Coupling of Ketyl Radicals with Arenes 1. T. Tanaka et al. CHEM. COMMUN. 2002, 316 2. H.-U. Reissig Synlett et al. 2001, 1290 1. H.-U.