Ligand-Free Copper-Catalyzed Negishi Coupling of Alkyl-, Aryl-, and Alkynylzinc Reagents with Heteroaryl Iodides

Angewandte Chemie - International Edition

Volumn 54, Issue 28, 2015, Pages 8236-8240

  Thapa, Surendra ^a   Kafle, Arjun ^a   Gurung, Santosh K ^a   Montoya, Adam ^a   Riedel, Patrick ^a   Giri, Ramesh ^a  

^a UNIVERSITY OF NEW MEXICO   (United States)

Author keywords

copper; cross coupling; heterocycles; synthetic methods; zinc

Indexed keywords

CATALYSIS; COPPER; LIGANDS; ZINC;

COPPER CATALYZED; CROSS-COUPLINGS; ELEVATED TEMPERATURE; HETEROCYCLES; LIGAND-FREE; NEGISHI COUPLING; ROOM TEMPERATURE; SYNTHETIC METHODS;

CHEMICAL REACTIONS;

EID: 85027952836     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201502379     Document Type: Article

References (88)

1. For reviews, see
2. F. Diederich, P. J. Stang, Metal-Catalyzed Cross-Coupling Reactions, Wiley-VCH, New York, 1998
3. E.-i. Negishi, Q. Hu, Z. Huang, M. Qian, G. Wang, Aldrichimica Acta 2005, 38, 71
4. G. C. Fu, Acc. Chem. Res. 2008, 41, 1555
5. Organozinc Reagents: A Practical Approach (Eds.:, P. Knochel, P. Jones,), Oxford University Press, Oxford, 1999.
6. For a review, see:, R. Jana, T. P. Pathak, M. S. Sigman, Chem. Rev. 2011, 111, 1417-1492.
7. L. Melzig, A. Metzger, P. Knochel, J. Org. Chem. 2010, 75, 2131-2133
8. A. Joshi-Pangu, M. Ganesh, M. R. Biscoe, Org. Lett. 2011, 13, 1218-1221
9. L. Melzig, T. Dennenwaldt, A. Gavryushin, P. Knochel, J. Org. Chem. 2011, 76, 8891-8906
10. L. Melzig, A. Gavryushin, P. Knochel, Org. Lett. 2007, 9, 5529-5532
11. T. Thaler, B. Haag, A. Gavryushin, K. Schober, E. Hartmann, R. M. Gschwind, H. Zipse, P. Mayer, P. Knochel, Nat. Chem. 2010, 2, 125-130
12. Y. Yang, K. Niedermann, C. Han, S. L. Buchwald, Org. Lett. 2014, 16, 4638-4641
13. M. Pompeo, R. D. J. Froese, N. Hadei, M. G. Organ, Angew. Chem. Int. Ed. 2012, 51, 11354-11357
14. Angew. Chem. 2012, 124, 11516-11519
15. Y. A. Getmanenko, R. J. Twieg, J. Org. Chem. 2008, 73, 830-839
16. T. Bach, S. Heuser, J. Org. Chem. 2002, 67, 5789-5795
17. I. Kondolff, H. Doucet, M. Santelli, Organometallics 2006, 25, 5219-5222
18. I. A. S. Walters, Tetrahedron Lett. 2006, 47, 341-344
19. A. Krasovskiy, C. Duplais, B. H. Lipshutz, J. Am. Chem. Soc. 2009, 131, 15592-15593.
20. M. R. Netherton, G. C. Fu, Adv. Synth. Catal. 2004, 346, 1525-1532
21. D. J. Cárdenas, Angew. Chem. Int. Ed. 2003, 42, 384-387
22. Angew. Chem. 2003, 115, 398-401.
23. K. Tamao, Y. Kiso, K. Sumitani, M. Kumada, J. Am. Chem. Soc. 1972, 94, 9268-9269
24. Y. Kiso, K. Tamao, M. Kumada, J. Organomet. Chem. 1973, 50, C 12 -C 14.
25. V. F. Slagt, A. H. M. deVries, J. G. deVries, R. M. Kellogg, Org. Process Res. Dev. 2009, 14, 30-47
26. K. Billingsley, S. L. Buchwald, J. Am. Chem. Soc. 2007, 129, 3358-3366.
27. J. Magano, J. R. Dunetz, Chem. Rev. 2011, 111, 2177-2250
28. M. Baumann, I. R. Baxendale, Beilstein J. Org. Chem. 2013, 9, 2265-2319.
29. C. Han, S. L. Buchwald, J. Am. Chem. Soc. 2009, 131, 7532-7533
30. J. Zhou, G. C. Fu, J. Am. Chem. Soc. 2003, 125, 14726-14727
31. C. Dai, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 2719-2724
32. T. Hayashi, M. Konishi, Y. Kobori, M. Kumada, T. Higuchi, K. Hirotsu, J. Am. Chem. Soc. 1984, 106, 158-163
33. N. Kataoka, Q. Shelby, J. P. Stambuli, J. F. Hartwig, J. Org. Chem. 2002, 67, 5553-5566.
34. For previous seminal works on ligand-free copper-catalyzed couplings of secondary and tertiary alkyl Grignard reagents, see
35. L. Hintermann, L. Xiao, A. Labonne, Angew. Chem. Int. Ed. 2008, 47, 8246-8250
36. Angew. Chem. 2008, 120, 8370-8374
37. D. H. Burns, J. D. Miller, H.-K. Chan, M. O. Delaney, J. Am. Chem. Soc. 1997, 119, 2125-2133
38. G. Cahiez, O. Gager, J. Buendia, Angew. Chem. Int. Ed. 2010, 49, 1278-1281
39. Angew. Chem. 2010, 122, 1300-1303.
40. S. K. Gurung, S. Thapa, A. S. Vangala, R. Giri, Org. Lett. 2013, 15, 5378-5381
41. S. K. Gurung, S. Thapa, A. Kafle, D. A. Dickie, R. Giri, Org. Lett. 2014, 16, 1264-1267
42. S. K. Gurung, S. Thapa, B. Shrestha, R. Giri, Synthesis 2014, 1933-1937
43. S. Thapa, S. K. Gurung, D. A. Dickie, R. Giri, Angew. Chem. Int. Ed. 2014, 53, 11620-11624
44. Angew. Chem. 2014, 126, 11804-11808
45. S. Thapa, P. Basnet, S. K. Gurung, R. Giri, Chem. Commun. 2015, 51, 4009-4012.
46. For additional examples of copper-catalyzed cross-couplings with organometallic reagents of Mg, B, Sn, and Si, see
47. C.-T. Yang, Z.-Q. Zhang, J. Liang, J.-H. Liu, X.-Y. Lu, H.-H. Chen, L. Liu, J. Am. Chem. Soc. 2012, 134, 11124-11127
48. J. Terao, A. Ikumi, H. Kuniyasu, N. Kambe, J. Am. Chem. Soc. 2003, 125, 5646-5647
49. G. D. Allred, L. S. Liebeskind, J. Am. Chem. Soc. 1996, 118, 2748-2749
50. J. R. Falck, R. K. Bhatt, J. Ye, J. Am. Chem. Soc. 1995, 117, 5973-5982
51. S.-K. Kang, J.-S. Kim, S.-C. Choi, J. Org. Chem. 1997, 62, 4208-4209
52. J.-H. Li, B.-X. Tang, L.-M. Tao, Y.-X. Xie, Y. Liang, M.-B. Zhang, J. Org. Chem. 2006, 71, 7488-7490
53. L. Cornelissen, M. Lefrancq, O. Riant, Org. Lett. 2014, 16, 3024-3027
54. A. Tsubouchi, D. Muramatsu, T. Takeda, Angew. Chem. Int. Ed. 2013, 52, 12719-12722
55. Angew. Chem. 2013, 125, 12951-12954
56. H. Taguchi, A. Tsubouchi, T. Takeda, Tetrahedron Lett. 2003, 44, 5205-5207
57. M. B. Thathagar, J. Beckers, G. Rothenberg, J. Am. Chem. Soc. 2002, 124, 11858-11859
58. J.-H. Li, J.-L. Li, D.-P. Wang, S.-F. Pi, Y.-X. Xie, M.-B. Zhang, X.-C. Hu, J. Org. Chem. 2007, 72, 2053-2057
59. Y. Zhou, W. You, K. B. Smith, M. K. Brown, Angew. Chem. Int. Ed. 2014, 53, 3475-3479
60. Angew. Chem. 2014, 126, 3543-3547
61. C.-T. Yang, Z.-Q. Zhang, Y.-C. Liu, L. Liu, Angew. Chem. Int. Ed. 2011, 50, 3904-3907
62. Angew. Chem. 2011, 123, 3990-3993
63. G. Cahiez, S. Marquais, Synlett 1993, 45-47
64. G. Cahiez, S. Marquais, Pure Appl. Chem. 1996, 68, 53-60
65. P. Ren, L.-A. Stern, X. Hu, Angew. Chem. Int. Ed. 2012, 51, 9110
66. Angew. Chem. 2012, 124, 9244
67. Also see: Ref.[9].
68. For reviews on copper-catalyzed couplings, see
69. I. P. Beletskaya, A. V. Cheprakov, Coord. Chem. Rev. 2004, 248, 2337-2364
70. G. Evano, N. Blanchard, M. Toumi, Chem. Rev. 2008, 108, 3054-3131
71. B. H. Lipshutz, Acc. Chem. Res. 1997, 30, 277-282
72. J. Hassan, M. Sévignon, C. Gozzi, E. Schulz, M. Lemaire, Chem. Rev. 2002, 102, 1359-1470.
73. H. K. Hofstee, J. Boersma, G. J. M. VanDerKerk, J. Organomet. Chem. 1978, 144, 255-261.
74. A. Krasovskiy, V. Malakhov, A. Gavryushin, P. Knochel, Angew. Chem. Int. Ed. 2006, 45, 6040-6044
75. Angew. Chem. 2006, 118, 6186-6190.
76. T. Hjelmgaard, D. Tanner, Org. Biomol. Chem. 2006, 4, 1796-1805.
77. For an example of the reaction of an alkylzinc reagent with allenyl bromide and alkynyl iodide in the presence of stoichiometric amounts of CuCN2 LiCl, see:, W. F. J. Karstens, M. J. Moolenaar, F. P. J. T. Rutjes, U. Grabowska, W. N. Speckamp, H. Hiemstra, Tetrahedron Lett. 1999, 40, 8629-8632
78. N2 process, see:, C. F. Malosh, J. M. Ready, J. Am. Chem. Soc. 2004, 126, 10240.
79. A. L. Hansen, J.-P. Ebran, T. M. Gøgsig, T. Skrydstrup, J. Org. Chem. 2007, 72, 6464-6472
80. H. N. Hunter, N. Hadei, V. Blagojevic, P. Patschinski, G. T. Achonduh, S. Avola, D. K. Bohme, M. G. Organ, Chem. Eur. J. 2011, 17, 7845-7851.
81. 2-filled glovebox. The product was formed in slightly lower yield (76 %) when the reaction was conducted with the standard Schlenk technique.
82. For previous examples of couplings using secondary alkyl Grignard reagents with copper catalysts, see: Refs. [9b-c, 11a,b]. For couplings with tertiary alkyl Grignard reagents with Cu-catalysts, see: Ref.[9]. For couplings with tertiary alkyl Grignard reagents with nickel catalysts, see
83. C. Lohre, T. Dröge, C. Wang, F. Glorius, Chem. Eur. J. 2011, 17, 6052-6055
84. A. Joshi-Pangu, C.-Y. Wang, M. R. Biscoe, J. Am. Chem. Soc. 2011, 133, 8478-8481.
85. For copper-catalyzed direct coupling of heteroarenes with aryl iodides, see
86. H.-Q. Do, O. Daugulis, J. Am. Chem. Soc. 2007, 129, 12404-12405
87. H.-Q. Do, R. M. K. Khan, O. Daugulis, J. Am. Chem. Soc. 2008, 130, 15185-15192.
88. Based on previous copper-catalyzed couplings (see Ref.[10]), the current reaction can be assumed to proceed by transmetalation followed by reaction with ArI. Since RZnX are known to undergo transmetalation with copper(I) salts below room temperature (see Ref.[13]), we believe that the reaction with ArI could be rate-limiting. In addition, alkylcopper(I) species are more electron-rich than aryl- and alkynylcopper(I) species and are more likely to react with ArI at lower temperatures than aryl- and alkynylcopper(I) species formed after transmetalation with alkyl-, aryl-, and alkynylzinc reagents.