Oxidative Couplings of Hydrocarbons
Oxidative couplings of two nucleophiles Oxidants involved: O 2 H 2 O 2 high h valent metals(copper salts) halides(iodine(Ⅲ) oxidants) Lei, A. W. Chem. Rev., 2011, 111, 1780 1824
Comparison with traditional couplings Danger: homocouplings
Couplings between two hydrocarbons Csp-HandCsp-Hasnucleophiles Csp-HandCsp 2 -Hasnucleophiles Csp-HandCsp 3 -Hasnucleophiles Csp 2 -HandCsp 2 -Hasnucleophiles Csp 2 -HandCsp 3 -Hasnucleophiles Csp 3 -HandCsp 3 -Hasnucleophiles
Csp-H and Csp-H as nucleophiles Glaser coupling(1869) homocoupling of terminal alkynes applied in the synthesis of conjugated diynes Diederich, F. Angew. Chem., Int. Ed. 2000, 39, 2632. Recent developments of homocouplings M: Pd, Ni, Fe Oxidant: molecular oxygen, I 2, α-halocarbonyl compounds
Csp-H and Csp-H as nucleophiles Cross-couplings of different alkynes: excess of one of the two alkynes to achieve cross-couplings speculated reaction pathways Lei, A. Org. Lett. 2009, 11, 709
Csp-H and Csp 2 -H as nucleophiles gold(Ⅲ) mediated reactions quantitative amounts of AuCl 3 needed Fuchita, Y. J. Chem. Soc., Dalton Trans. 2001, 2330
Csp-H and Csp 2 -H as nucleophiles electron-deficient alkynes electron-rich arenes Mechanistic proposal for the Au-catalyzed ethynylation of arenes Nevado, C. J. Am. Chem. Soc. 2010, 132, 1512
Csp-H and Csp 2 -H as nucleophiles electron-deficient polyfluoroarenes terminal alkynes Su,W. J. Am. Chem. Soc. 2010, 132, 2522.
Csp-H and Csp 2 -H as nucleophiles Miura,M. Org. Lett. 2010, 12, 2358 Li, C. J. Chem. Commun. 2010, 46, 4184
Csp-H and Csp 2 -H as nucleophiles Li, C. J. Chem. Commun. 2010, 46, 4184
Csp-H and Csp 3 -H as nucleophiles sp 3 carbon normally has to be adajcent to a heteroatom such as nitrogen terminal alkynes Miura, M. J. Chem. Res., Synop. 1993, 434 Li, C. J. J. Am. Chem. Soc. 2004, 126, 11810
Csp-H and Csp 3 -H as nucleophiles Li, C. J. J. Am. Chem. Soc. 2004, 126, 11810
Csp-H and Csp 3 -H as nucleophiles Li, C. J. Org. Lett. 2004, 6, 4997
Csp-H and Csp 3 -H as nucleophiles aliphatic tertiary methyamines no desired cross-couplling product observed Li, X. Org. Lett. 2009, 11, 1027
Csp-H and Csp 3 -H as nucleophiles Li, X. Org. Lett. 2009, 11, 1027
Csp-H and Csp 3 -H as nucleophiles secondary amines R 1 group vital to the tansforamtion Li, C. J. Angew. Chem., Int. Ed. 2008, 47, 7075
Csp-H and Csp 3 -H as nucleophiles functionalization of glycine derivatives Li, C. J. Angew. Chem., Int. Ed. 2008, 47, 7075
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Earliest: homocoupling of benzene in the presence of stoichiometric amounts of fpdcl 2 and sodium acetate t in acetic acid as the solvent van Helden, R.; Verberg, G. Recl. Trav. Chim. Pays-Bas 1965, 84, 1263 Later: metals:hg(Ⅱ), Tl(Ⅲ), Fe(Ⅲ), Cu(Ⅱ), Pd(Ⅱ), Au(Ⅲ) peroxocobalt(iii) species, Co(III) OO Co(III), could be generated the exact role of each metallic salt was unclear Pd(0) with this species could give a Pd(II) peroxo complex Sasson, Y. Adv. Synth. Catal. 2001, 343, 455 Tse, M. K. J. Organomet. Chem. 2009, 694, 524
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Silver salt was essential Mori, A. J. Am. Chem. Soc. 2004, 126, 5074
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Qian,W.; Bao,W.Org. Biomol. Chem. 2010, 8,326
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Daugulis, O. Org. Lett. 2010, 12, 1200 excellent regioselectivity Zhang, Y. J. Org. Chem. 2010, 75, 170
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Sanford,M. S. J. Am. Chem. Soc. 2006, 128, 14047
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Deng, G.; Li, C. J. Adv. Synth. Catal. 2009, 351, 2071
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Katsuki, T. J. Am. Chem. Soc. 2010, 132, 13633
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Katsuki, T. J. Am. Chem. Soc. 2010, 132, 13633
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: low yields but high selectivities Lu, W. Organometallics 2006, 25, 5973 pyridine additive may be acting to stabilize the palladium(0) before reoxidation Fagnou, K. Si Science 2007, 316, 1172
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: removal of the pyridine additive and the change of N-acetyl with N- pivaloyl resulted in complete conversion and high selectivity Fagnou, K. J. Am. Chem. Soc. 2007, 129, 12072 DeBoef, B. Org. Lett. 2007, 9, 3137
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: DeBoef, B. Tetrahedron Lett. 2008, 49, 4050 DFT suggests that the abstraction of hydrogen from thiophene should first take place in the reaction system, yet the second C H metalation toward homocoupling product is unfavorable compared to the metalation ti toward crosscoupling so as to give the desired product Hu,C.; You, J. J. Am. Chem. Soc. 2010, 132, 1822
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Zhang, X. J. Am. Chem. Soc. 2010, 132, 12850 Su, W. J. Am. Chem. Soc. 2010, 132, 16377
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Chang, S. J. Am. Chem. Soc. 2008, 130, 9254
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Sanford, M. S. J. Am. Chem. Soc. 2007, 129, 11904 Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 9651
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Shi, Z. J. Angew. Chem., Int. Ed. 2008, 47, 1115 R 1 =Pv Buchwald, S. L. Org. Lett. 2008, 10, 2207
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Both trifluoroacetyl (TFA) and sodium persulfate were found to be critical in achieving high efficiency for the transformation Dong, V. M. J. Am. Chem. Soc. 2010, 132, 5837
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Fujiwara, Y. Tetrahedron Lett. 1967, 1119
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Normally, the oxidative cross-couplings take place at the 2- and 5-positions of fivemembered heteroarenes and at tthe 3-position for indoles Fujiwara, Y. Org. Lett. 1999, 1, 2097
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: solvent-controlled process Gaunt, M. J. Angew. Chem., Int. Ed. 2005, 44, 3125
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: acidic conditions slowed down the deprotonation of the first palladation of the indole species and allowed the migration of the C3 PdX bond to the C2-position, resulting in the formation of C2 alkenylation products Gaunt, M. J. Angew. Chem., Int. Ed. 2005, 44, 3125
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Ricci, A. Chem. Commun. 2005, 1854
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Gaunt, M. J. J. Am. Chem. Soc. 2006, 128, 2528
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: base additive Chang, S. J. Am. Chem. Soc. 2008, 130, 9254
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: de Vries, J. G.; van Leeuwen, P. W. N. M. J. Am. Chem.Soc. 2002, 124, 1586 Prasad, K. Adv.Synth. Catal. 2005, 347, 1921
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Liu, L.; Guo, Q.-X. Tetrahedron Lett. 2007, 48, 5449 Lipshutz, B. H. Org. Lett. 2010, 12, 1972
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Glorius, F. J. Am. Chem. Soc. 2010, 132, 9982
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Yu, J. Q. Angew. Chem., Int. Ed. 2008, 47, 6452
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: ligands enable both reactivity and selectivity Yu, J.-Q. Science 2010, 327, 315
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Yu, J. Q. Angew. Chem., Int. Ed. 2010, 49, 6169 a change in the mechanism of C H cleavage from electrophilic palladation to proton abstraction Yu, J. Q. J. Am. Chem. Soc. 2010, 132, 14137
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: electron-deficient arenes Yu, J. Q. J. Am. Chem. Soc. 2009, 131, 5072
Csp 2 -H and Csp 2 -H as nucleophiles Couplings between alkenes: Gusevskaya, E. V. J. Organomet. Chem. 2004, 689, 302
Csp 2 -H and Csp 3 -H as nucleophiles Normally, the Csp 2 H of aromatic arenes is less active than the Csp H of terminal alkynes. Even so, the oxidative coupling between Csp 2 H and Csp 3 HH was achieved by using a similar protocol as the coupling between Csp H and Csp 3 H. Li, C. J. J. Am. Chem. Soc. 2005, 127, 6968
Csp 2 -H and Csp 3 -H as nucleophiles Itami, K. Chem. Asian. J. 2009, 4, 1416 Che, C. M. Chem. Commun. 2010, 46, 2739
Csp 2 -H and Csp 3 -H as nucleophiles CuBr 2 was more efficient than CuBr Li, C. J. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 892
Csp 2 -H and Csp 3 -H as nucleophiles Bao, W. Adv. Synth. Catal. 2009, 351, 2845
Csp 2 -H and Csp 3 -H as nucleophiles Li, C. J. Angew. Chem., Int. Ed. 2008, 47, 6278
Csp 2 -H and Csp 3 -H as nucleophiles Li, C. J. Org. Lett. 2009, 11, 1171
Csp 3 -H and Csp 3 -H as nucleophiles Li and co-workers have developed a general cross-dehydrogenative coupling (CDC) Li, C. J. Eur. J. Org. Chem. 2005, 3173 Li, C. J. J. Am. Chem. Soc. 2005, 127, 3672
Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Angew. Chem., Int. Ed. 2006, 45, 1949 Li, C. J. J. Am. Chem. Soc. 2006, 128, 56
Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Angew. Chem., Int. Ed. 2007, 46, 6505 Li, C. J. Eur. J. Org. Chem. 2007, 4654
Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Green. Chem. 2007, 9, 1047 Li, C. J. Angew. Chem., Int. Ed. 2008, 47, 7075
Csp 3 -H and Csp 3 -H as nucleophiles Shi, Z. J. J. Am. Chem. Soc. 2008, 130, 12901 Powell, D. A. J. Org. Chem. 2008, 73, 7822
Csp 3 -H and Csp 3 -H as nucleophiles Xiang, J. N. Catal. Commun. 2009, 11, 162 Tan, Z.; Guo, C. C. Chem. Commun. 2009, 953
Csp 3 -H and Csp 3 -H as nucleophiles Klussmann, M. Chem. Commun. 2009, 3169 Gong, L. Z. Angew. Chem., Int. Ed. 2010, 49, 5558
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Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Acc. Chem. Res. 2009, 42, 335
Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Acc. Chem. Res. 2009, 42, 335
Prospect scopeofsubstrates chemo-,regio-,enantio-selectivities oxidants:metal?molecularoxygen?air loadingofcatalysts