金属钴（ Co ）参与的光化学反应 ( 最近 30 年的进展）

金属钴（Co）参与的光化学反应(最近30年的进展）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

Organocobalt CoII (salophen) Cobaloxime BrCoIII (salen)PPh3 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.

二. Organocobalt-Mediated Radical Reactions 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

(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

串联 (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

Branchaud, B. P.J. Org. Chem. 1988,53, 4641.

C=N 键加成 • Bruce P. Branchaud Tetrahedron Letters, 1988.29,6545. • (b) Bruce P. Branchaud Tetrahedron Letters, 1991.32, 3639.

(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; Bruce P. Branchaud,Tetrahedron Letters, 1997,38, 7009,

(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. TetrahedronLett.. 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.

三. Inorganocobalt-Mediated Radical Reactions 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.

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.

two 460 W lamps (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 C. Aubert, M. Malacria. Org. Lett. 2004. 6, 3937.

K. Peter C. Vollhardt, Synlett,1989, 15. Marko Hapke, J. Org. Chem. 2010, 75, 3993.

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. 2091.

Caubere. P. J. Org. Chem. 1983, 48, 1166. Caubere. P.. J. Org. Chem. 1983,48, 1919.

机理 Vincent Gandon, Max Malacria, and Corinne Aubert. Organometallics 2007, 26, 819.

金属钴（ Co ）参与的光化学反应 ( 最近 30 年的进展）