金属有机化学三.ppt

1、龚流柱 中国科学技术大学合肥微尺度物质科学国家实验室，化学系,Gold Catalysis,金属有机化学-均相催化，2010-11-23,General Introduction of Gold,Atomic Number: 79 Atomic Weight: 196.966569 Common Oxidation State: +3, +1,Electron Shell Configuration:,1s2, 2s2 2p6, 3s2 3p6 3d10, 4s2 4p6 4d10 4f14, 5s2 5p6 5d10,5f0 6s1 6p0,Au(I) and Au(III) are abl

2、e to form complexes with heteroatom and unsaturated Hydrocarbons,-Complexes of Gold in Any of Its Oxidation States,Chalk, A. J. Am. Chem. Soc. 1964, 86, 4733 Strahle, J. and Calderazzo, F. et al, Organometallics 1987, 6, 1207 Mingos, D. M. P. et al, Angew. Chem. Int. Ed. Engl. 1995, 34, 1894.,Nesmey

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4、. ; Sawamura, M.; Ito, Y. Tetrahedron 1992, 48, 1999.,Hydrosilylation of Aldehydes and Imines,Hosomi, A. et al, Chem. Commun. 2000, 981-982,Ketones could not be reduced.,Activation of Alkynes for Nucleophilic Addition,General Concept,First example of Hydrooxylation of Alkynes,Reaction Mechanism,P-Le

5、wis Acid,Proton Transfer,Norman, R. O. C.; Parr, W. J. E.; Thomans, C. B. J. Chem. Soc. Perkin. Trans. 1, 1976, 1983,Intramolecular Alcohol Addition to Carbon-Carbon Triple Bond,Reaction Mechanism,Antoniotti, S.; Genin, E.; Micheler, V.; Gent, J.-P. J. Am. Chem. Soc. 2005, 127, 9976,Rearrangement fo

6、r the Synthesis of Piperidin-4-ones,Cui, L.; Peng, Y.; Zhang, L. J. Am. Chem. Soc. 2009, 131, 8394-8395,Generation of Gold Carbenes for the Synthesis of Dihydrofuran-3-ones,Zhang, L. et al, J. Am. Chem. Soc. 2010, 132, 3258-3259,Synthesis of A-D Ring of Azaspiracid,Synthetic Approach,Mukaiyama Oxida

7、tive cyclization: Inoki, S.; Mukaiyama, T. Chem. Lett. 1990, 67-70,modp = 1-morpholinocarbamoyl-4,4-dimethyl -1,3-pentanedionato,Li, Y.; Zhou, F.; Forsyth, C. J. Angew. Chem. Int. Ed. 2007, 46, 279,Hydroxylation/ Prins Cyclization,Barluenga, J. et al, Angew. Chem. Int. Ed. 2006, 45, 2091,Hydrocarbox

8、ylation of Alkynes,Genet, J.-P. et al, J. Am. Chem. Soc. 2006, 128, 3112,Carboalkoxylation of Alkynes,Possible Mechanism,Cross-Reaction,Reaction of Enantioenriched Substrates,Reaction Mechanism,Dube, P.; Toste, D. F. J. Am. Chem. Soc. 2006, 128, 12062,Intramolecular Hydroamination of Alkynes,Fukuda,

9、 Y.; Utimoto, K.; Nozaki, H. Heterocycles 1987, 25, 297; Fukuda, Y.; Utimoto, K. Synthesis 1991, 975,Mizushima, E.; Hayashi, T.; Tanaka, M. Org. Lett. 2003, 5, 3349 Luo, Y.; Li, Z.; Li, C.-J. Org. Lett. 2005, 7, 2675,Addition of Carbonyls to Alkynes,Hashmi, A. S. K. et al, Angew. Chem. Int. Ed. 2000

10、, 39, 2285,Kirsch, S. F. et al, Angew. Chem. Int. Ed. 2006, 45, 5878,Zhang, J.; Schmalz, H.-G. Angew. Chem. Int. Ed. 2006, 45, 6704,Yao, T.; Zhang, X.; Larock, R. J. Am. Chem. Soc. 2004, 126, 11164,Dyker, G.; Hildebrandt, D.; Liu, J.; Merz, K. Angew. Chem. Int. Ed. 2003, 42, 4399,Addition of Imine t

11、o Alkynes,Zhang, Y.; Donahue, J. P.; Li, C.-J. Org. Lett. 2007, 9, 627,Kusuma, H.; Miyashita, Y.; Takaya, Iwasawa, N. Org. Lett. 2006, 8, 289,Afonsi, M. et al, J. Org. Chem. 2005, 70, 2265,Gorin, D. J.; Davis, N. R.; Toste, F. D. J. Am. Chem. Soc. 2005, 127, 11260,Addition of Azide,Addition of Enol

12、Ethers and Enamines,Sherry, B. D.; Maus, L.; Laforteza, B. N.; Toste, F. D. J. Am. Chem. Soc. 2006, 128, 8132,Aryl Addition to Alkynes,Ferrer, C.; Echavarren, A. M. Angew. Chem. Int. Ed. 2006, 45, 1105,Shi, Z.; He, C. J. Org. Chem. 2004, 69, 3669.,Amination of Allenes,Reaction Mechanism,Nishina, N.;

13、 Yamamoto, Y. Angew. Chem. Int. Ed. 2006, 45, 3314,Liu, Z.; wasmuth, A. S.; Nelson, S. G. J. Am. Chem. Soc. 2006, 128, 10352,Hashmi, A. S. K. et al, Angew. Chem. Int. Ed. 2000, 39, 2285,He, C. et al, J. Am. Chem. Soc. 2006, 128, 1798,He, C. et al, J. Am. Chem. Soc. 2005, 127, 673,Enynes as Substrate

14、s,Hashimi, A. S. K. et al, J. Am. Chem. Soc. 2000, 122, 11553 Echavarren, A. M. et al, Angew. Chem. Int. Ed. 2001, 40, 4754; J. Am. Chem. Soc. 2001, 123, 10511,Echavarren, A. M. et al, Angew. Chem. Int. Ed. 2004, 43, 2402,Luzung, M. R.; Markham, J. P.; Toste, F. D. J. Am. Chem. Soc. 2004, 126, 10858

15、,Cascade Reaction,Reaction Mechanism,Zhang, L.; Kozmin, S. A. J. Am. Chem. Soc. 2005, 127, 6962,Toste, F. D. et al, J. Am. Chem. Soc. 2010, 132, 8276-8277,Polycyclization Reaction Catalyzed by Gold(I),He, C. et al, J. Am. Chem. Soc. 2006, 128, 1798,Functionalization of Alkenes,He, C. et al, J. Am. C

16、hem. Soc. 2005, 127, 673,Oxidative Carbafunctionalization of Alkenes,Zhang, L. et al, J. Am. Chem. Soc. 2010, 132, 1474-1475,Reaction Mechanism,Zhang, L. et al, J. Am. Chem. Soc. 2010, 132, 1474-1475,Olefin Metathesis Mechanism, Catalyst Design and Application,Metathesis:,Metathesis:,History of Olef

17、in Metathesis,Truett, W. L.; et al, J. Am. Chem. Soc. 1960, 2337-2340,The First polymerization of Nobornene,Reaction Mechanism,Calderon, N. et al, J. Am. Chem. Soc. 1968, 90, 4133-4140 Lewandos, G. S.; Pettit, R. J. Am. Chem. Soc. 1971, 93, 7087-7088 Grubbs, R. H.; Brunck, T. K. J. Am. Chem. Soc. 19

18、72, 94, 2538-2540,Chauvins Mechanism,Chauvin, Y.; Herisson, J.-L. Makromol. Chem. 1971, 141, 161.,Metal Carbene Mediated Olefin Metathesis,Casey, C. P.; Burkhardt, T. J. J. Am. Chem. Soc. 1974, 96, 7808-7809,Tebbe Reagent for Metathesis,Tebbe, F. N. et al, J. Am. Chem. Soc. 1978, 100, 3611-3613,Grub

19、bs, R. H. et al, J. Am. Chem. Soc. 1980, 102, 7491,Gilliom, L. R.; Grubbs, R. H. J. Am. Chem. Soc. 1986, 108, 733-742,Application to the Synthesis of Capnellene,Stille, J. R.; Grubbs, R. H. J. Am. Chem. Soc. 1986, 108, 855-856,过渡金属卡宾,金属卡宾（Metal Carbenes，直译为金属碳烯）是指金属与一个二取代的碳中心相连的络合物,1) Fischer卡宾：是单线态

20、卡宾，具有亲电活性,Fischer卡宾发生的反应,正反2+2反应,Michael加成,1) Schrock卡宾：是三线态卡宾，具有亲核活性,亲核卡宾发生的反应,Nb, Mo, and W Carbene Complexes for metathesis,For a review: Astruc, D. New. J. Chem. 2005, 29, 42-56,More catalytically active, but Less functionality tolerant,Grubbs Ruthenium Metathesis Catalysts, Air-Stable and Compatible with Most Functional Groups,金属卡宾催化的烯烃复分解反应 (2005 Nobel Prize),Richard R. Schrock,Yves Chauvin,Robert H. Grubbs,交叉复分解反应(Cross-Metathes