Oxidative couplings of two nucleophiles

Transcription

1 Oxidative Couplings of Hydrocarbons

2 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,

3 Comparison with traditional couplings Danger: homocouplings

4 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

5 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, Recent developments of homocouplings M: Pd, Ni, Fe Oxidant: molecular oxygen, I 2, α-halocarbonyl compounds

6 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

7 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

8 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

9 Csp-H and Csp 2 -H as nucleophiles electron-deficient polyfluoroarenes terminal alkynes Su,W. J. Am. Chem. Soc. 2010, 132, 2522.

10 Csp-H and Csp 2 -H as nucleophiles Miura,M. Org. Lett. 2010, 12, 2358 Li, C. J. Chem. Commun. 2010, 46, 4184

11 Csp-H and Csp 2 -H as nucleophiles Li, C. J. Chem. Commun. 2010, 46, 4184

12 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

13 Csp-H and Csp 3 -H as nucleophiles Li, C. J. J. Am. Chem. Soc. 2004, 126, 11810

14 Csp-H and Csp 3 -H as nucleophiles Li, C. J. Org. Lett. 2004, 6, 4997

15 Csp-H and Csp 3 -H as nucleophiles aliphatic tertiary methyamines no desired cross-couplling product observed Li, X. Org. Lett. 2009, 11, 1027

16 Csp-H and Csp 3 -H as nucleophiles Li, X. Org. Lett. 2009, 11, 1027

17 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

18 Csp-H and Csp 3 -H as nucleophiles functionalization of glycine derivatives Li, C. J. Angew. Chem., Int. Ed. 2008, 47, 7075

19 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

20 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

21 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Qian,W.; Bao,W.Org. Biomol. Chem. 2010, 8,326

22 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

23 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Sanford,M. S. J. Am. Chem. Soc. 2006, 128, 14047

24 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Deng, G.; Li, C. J. Adv. Synth. Catal. 2009, 351, 2071

25 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Katsuki, T. J. Am. Chem. Soc. 2010, 132, 13633

26 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Katsuki, T. J. Am. Chem. Soc. 2010, 132, 13633

27 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

28 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, DeBoef, B. Org. Lett. 2007, 9, 3137

29 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

30 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Zhang, X. J. Am. Chem. Soc. 2010, 132, Su, W. J. Am. Chem. Soc. 2010, 132, 16377

31 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Chang, S. J. Am. Chem. Soc. 2008, 130, 9254

32 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes: Sanford, M. S. J. Am. Chem. Soc. 2007, 129, Sanford, M. S. J. Am. Chem. Soc. 2009, 131, 9651

33 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

34 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

35 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Fujiwara, Y. Tetrahedron Lett. 1967, 1119

36 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

37 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

38 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

39 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Ricci, A. Chem. Commun. 2005, 1854

40 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Gaunt, M. J. J. Am. Chem. Soc. 2006, 128, 2528

41 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

42 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

43 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

44 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Glorius, F. J. Am. Chem. Soc. 2010, 132, 9982

45 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between arenes and alkenes: Yu, J. Q. Angew. Chem., Int. Ed. 2008, 47, 6452

46 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

47 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

48 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

49 Csp 2 -H and Csp 2 -H as nucleophiles Couplings between alkenes: Gusevskaya, E. V. J. Organomet. Chem. 2004, 689, 302

50 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

51 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

52 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

53 Csp 2 -H and Csp 3 -H as nucleophiles Bao, W. Adv. Synth. Catal. 2009, 351, 2845

54 Csp 2 -H and Csp 3 -H as nucleophiles Li, C. J. Angew. Chem., Int. Ed. 2008, 47, 6278

55 Csp 2 -H and Csp 3 -H as nucleophiles Li, C. J. Org. Lett. 2009, 11, 1171

56 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

57 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

58 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

59 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

60 Csp 3 -H and Csp 3 -H as nucleophiles Shi, Z. J. J. Am. Chem. Soc. 2008, 130, Powell, D. A. J. Org. Chem. 2008, 73, 7822

61 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

62 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

63 Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 8928

64 Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Acc. Chem. Res. 2009, 42, 335

65 Csp 3 -H and Csp 3 -H as nucleophiles Li, C. J. Acc. Chem. Res. 2009, 42, 335

66 Prospect scopeofsubstrates chemo-,regio-,enantio-selectivities oxidants:metal?molecularoxygen?air loadingofcatalysts