金属钴Co参与光化学反应最近30年进展.ppt

金属钴（Co）参与的光化学反应(最近30年的进展）,任磊（2012.04.14） 龚流柱课题组,钴是一种化学元素，符号为Co，原子序数27，属过渡金属，具有磁性。1735年瑞典化学家布兰特（G.Brandt）制出金属钴。 钴的英文名称“Cobalt”来自于德文的Kobold，意为“坏精灵”，因为钴矿有毒，矿工、冶炼者常在工作时染病，钴还会污染别的金属，这些不良效果过去都被看作精灵的恶作剧,Vitamin B12,BrCoIII (salen)PPh3,CoII (salophen),Cobaloxime,Organocobalt,Inorganocobalt,一. Vitamin B12 Catalyred Radical Reactions,Scheffold, R.; Abrecht, S.; Orlinski, R.; Hans-Rudolf, R.; Stamouli, P.; Tinembart, 0.; Walder, L.; Weymuth, C. Pure Appl. Chem. 1987, 59, 363.,Scheffold, R.; Orlinski, R. J. Am. Chem. Soc. 1983, 105, 7200.,Orlinski, R.; Stankiewicz, T. Tetrahedron Lett. 1988, 29, 1601.,1.偶联反应（Heck-type） 2.C=N键的加成反应 3.氧化化反应 4.傅克反应 5.其他反应,二. Organocobalt-Mediated Radical Reactions,(a) Schrauzer, G. N.；Windgassen，R. J. J. Am.Chem. Soc., 1966, 88, 3738. (b) Branchaud, B. P. J. Org. Chem. 1987,52, 212-217.,Branchaud, B. P. Tetrahedron Lett, , 1988, 29, 167.,Branchaud, B. P. J. Org. Chem. 1989,54. 1320.,机理,Branchaud, B. P. Tetrahedron Lett., 1988,.29,6037.,Branchaud, B. P. Tetrahedron.Lett.1991, 32, 6273.,Branchaud, B. P. Bio. Med. Chem. Lett. 1996, 6, 2289.,Carreira, E. M. Angew. Chem. Int. Ed. 2011, 50,11125,(a) Branchaud, B. P. Tetrahedmn Lett., 1994,35. 4071., (b) Branchaud, B. P. Tetrahedron Lett., 1993,34. 7885. (c) Branchaud, B. P. J. Org. Chem. 1998, 63. 3544,串联,Branchaud, B. P. J. Org. Chem. 1988,53, 4641.,Bruce P. Branchaud Tetrahedron Letters, 1988.29,6545. (b) Bruce P. Branchaud Tetrahedron Letters, 1991.32, 3639.,C=N 键加成,Bruce P. Branchaud, Tetrahedron Letters, 1997,38, 7009,(a) V. F. Patel. G. Pattenden. and J. J. Russell, Tetrahedron Lett 1986. 27. 2303 (b) H. Bhandal. G. Pattenden. and J. J. Russell. Tetrahedron Lett 1986, 27. 2299;,(a) D. J. Coveney, V. F. Patel, and G. Pattenden, Tetrahedron Lett., 1987, 28, 5949. (b) Vinod F. Patel and Gerald Pattenden, Tetrahedron Lett., 1988,29, 707.,100 W sunlamp,(a) V. F. Patel. G. Pattenden. and J. J. Russell, Tetrahedron Lett 1986. 27. 2303; (b) H. Bhandal. G. Pattenden. and J. J. Russell. Tetrahedron Lett 1986, 27. 2299; (c) M. Ladlow and G. Pattenden. ihicl 1983. 25, 4317;(d) M. J. Begley, M. Ladlow. and G. Pattenden, .Chem. Soc., Perkin Trcins. I , 1988, 1095.,Richard A. Earl and K. Peter C. Vollhardt. J. Am. Chem. Soc. 1983, 105, 6993.,(a) Aalbersberg, W. G. L.; Barkovich, A. J.; Funk, R. L.; Hilliard, R. L., III; Vollhardt, K. P. C. J. Am. Chem. Soc. 1975,97,5600; (b) Hilliard, R. L., 111; Vollhardt. K. P. C. J. Am. Chem. Soc. 1977,99,4058; c)Halter“, R. L.; Nguyen, N. H.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1985,107, 1379.,三. Inorganocobalt-Mediated Radical Reactions,Gesing, E. R. F.; Tane, J. P.; Vollhardt, K. P. C. Angew. Chem. Int. Ed. 1980,19, 1023.,Brian L. Pagenkopf and Tom Livinghouse, J. Am. Chem. Soc. 1996, 118, 2285.,(a) Vollhardt, K.P.C. Angew.Chem.,Int. Ed.1984,23,539;(b)Barbara Heller, J. Org. Chem. 2002, 67, 4414-4422;(c) Barbara Heller, J. Org. Chem. 2003, 68, 9221-9225; (d)Pilar Prieto, Jos Ignacio Garca, Chem. Eur. J. 2012, ASAP,two 460 W lamps,C. Aubert, M. Malacria. Org. Lett. 2004. 6, 3937.,Marko Hapke, J. Org. Chem. 2010, 75, 3993.,K. Peter C. Vollhardt, Synlett, 1989, 15.,Malacria, M.; Vollhardt, K. P. C. J. Org. Chem. 1984, 49,5010,(a) Sheward, G. S.; Vollhardt, K. P. C. J. Org. Chem.1986,51,5491;(b) Grotjahn, D. B.; Vollhardt, K. P. C. J. Am. Chem. Soc. 1986,108