Ligand-Controlled Regiodivergent Cu-Catalyzed Aminoboration of Unactivated Terminal Alkenes

Journal of the American Chemical Society

Volumn 137, Issue 20, 2015, Pages 6460-6463

  Sakae, Ryosuke ^a   Hirano, Koji ^a   Miura, Masahiro ^a  

^a OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; LIGANDS; ORGANIC COMPOUNDS;

AMINO GROUP; CU-CATALYSTS; DIBORON REAGENT; N-HETEROCYCLIC CARBENES; REGIOISOMERS; TERMINAL ALKENES; XANTPHOS;

HYDROCARBONS;

ALKENE DERIVATIVE; BORON; CARBENE; COPPER; HYDROXYLAMINE; LIGAND;

AMINOBORATION; ARTICLE; ASYMMETRIC CATALYSIS; CATALYSIS; CATALYST; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; CONTROLLED STUDY; STEREOCHEMISTRY;

EID: 84930216586     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/jacs.5b02775     Document Type: Article

References (51)

1. Müller, T. E.; Hultz, K. C.; Yus, M.; Foubelo, F.; Tada, M. Chem. Rev. 2008, 108, 3795
2. Minatti, A.; Muñiz, K. Chem. Soc. Rev. 2007, 36, 1142
3. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B. Chem. Rev. 1994, 94, 2483
4. Nilov, D.; Reiser, O. Adv. Synth. Catal. 2002, 344, 1169
5. Muñiz, K. Chem. Soc. Rev. 2004, 33, 166
6. Jensen, K. H.; Sigman, M. S. Org. Biomol. Chem. 2008, 6, 4083
7. McDonald, R. I.; Kiu, G.; Stahl, S. S. Chem. Rev. 2011, 111, 2981
8. Michaelis, D. J.; Shaffer, C. J.; Ischay, M. A.; Yoon, T. P. J. Am. Chem. Soc. 2007, 129, 1866
9. Liwosz, T. W.; Chemler, S. R. J. Am. Chem. Soc. 2012, 134, 2020
10. Egami, H.; Kawamura, S.; Miyazaki, A.; Sodeoka, M. Angew. Chem., Int. Ed. 2013, 52, 7841
11. Williamson, K. S.; Yoon, T. P. J. Am. Chem. Soc. 2010, 132, 4570
12. Williamson, K. S.; Yoon, T. P. J. Am. Chem. Soc. 2012, 134, 12370
13. Liu, G.-S.; Zhang, Y.-Q.; Yuan, Y.-A.; Xu, H. J. Am. Chem. Soc. 2013, 135, 3343
14. Lu, D.-F.; Zhu, C.-J.; Jia, Z.-X.; Xu, H. J. Am. Chem. Soc. 2014, 136, 13186
15. Yoon reported a metal-dependent regiodivergent oxyamination of styrenes. See ref 4a, 5a, 5b.
16. Jang, H.; Zhugralin, A. R.; Lee, Y.; Hoveyda, A. H. J. Am. Chem. Soc. 2011, 133, 7859
17. Tani, Y.; Fujihara, T.; Terao, J.; Tsuji, Y. J. Am. Chem. Soc. 2014, 136, 17706
18. Kawano, T.; Hirano, K.; Satoh, T.; Miura, M. J. Am. Chem. Soc. 2010, 132, 6900
19. Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2012, 51, 3642
20. Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2012, 51, 11827
21. Miki, Y.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2013, 52, 10830
22. Erdik, E.; Ay, M. Chem. Rev. 1989, 89, 1947
23. Narasaka, K.; Kitamura, M. Eur. J. Org. Chem. 2005, 21, 4505
24. Ciganek, E. Org. React. 2009, 72, 1
25. Barker, T. J.; Jarvo, E. R. Synthesis 2011, 3954
26. Berman, A. M.; Johnson, J. S. J. Am. Chem. Soc. 2004, 126, 5680
27. Campbell, M. J.; Johnson, J. S. Org. Lett. 2007, 9, 1521
28. Mlynarski, S. N.; Karns, A. S.; Morken, J. P. J. Am. Chem. Soc. 2012, 134, 16449
29. Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. J. Am. Chem. Soc. 2013, 135, 4934
30. Sakae, R.; Matsuda, N.; Hirano, K.; Satoh, T.; Miura, M. Org. Lett. 2014, 16, 1228
31. Sakae, R.; Hirano, K.; Satoh, T.; Miura, M. Angew. Chem., Int. Ed. 2015, 54, 613
32. Hirano, K.; Miura, M. Pure Appl. Chem. 2014, 86, 291
33. Semba, K.; Fujihara, T.; Terao, J.; Tsuji, Y. Tetrahedron 2015, 71, 2183
34. Kubota, K.; Yamamoto, E.; Ito, H. J. Am. Chem. Soc. 2013, 135, 2635
35. Kageyuki, I.; Yoshida, H.; Takaki, K. Synthesis 2014, 46, 1924
36. Iwadate, N.; Suginome, M. J. Am. Chem. Soc. 2010, 132, 2548
37. Yoshida, H.; Takemoto, Y.; Takaki, K. Chem. Commun. 2014, 50, 8299
38. Yoshida, H.; Takemoto, Y.; Takaki, K. Asian J. Org. Chem. 2014, 3, 1204
39. We preliminary found the unique activity of xantphos (ref 11a). See the SI for detailed optimization studies.
40. Lambert, J. B.; Zhao, Y.; Emblidge, R. W.; Salvador, L. A.; Liu, X.; So, J.-H.; Chelius, E. C. Acc. Chem. Res. 1999, 32, 183
41. Alabugin, I. V.; Gilmore, K. M.; Peterson, P. W. WIREs Comput. Mol. Sci. 2011, 1, 109
42. Unfortunately, styrene gave the terminally boryrated product even under conditions B.
43. Wang, J.-Y.; Wang, D.-X.; Zheng, Q.-Y.; Huang, Z.-T.; Wang, M.-X. J. Org. Chem. 2007, 72, 2040
44. Wood, J. L.; Marciasini, L. D.; Vaultier, M.; Pucheault, M. Synlett 2014, 25, 551 Unfortunately, pinB-Bdan did not work well under conditions A
45. The reaction of allylbenzene (1h) with O -benzoyl- N, N -diethylhydroxylamine (2b) under conditions B gave the moderate regioselectivity (3hb-Bdan: 4hb-Bdan = 22:78), which is similar to that of entry 8 in Table 2.
46. We have no explanation for the reason at present.
47. Ito, H.; Miya, T.; Sawamura, M. Tetrahedron 2012, 68, 3423
48. Dang, Li.; Zhao, H.; Lin, Z.; Marder, T. B. Organometallics 2007, 26, 2824
49. Clavier, H.; Nolan, S. P. Chem. Commun. 2010, 46, 841
50. The regioselectivity is less dependent on the electrophiles: the control experiments with MeOH in place of the hydroxylamine 2 resulted in a similar regioselectivity (see the SI for details). However, we cannot completely exclude the possibility that the borylcupration is reversible and the subsequent C-N forming step controls the overall regiochemical outcome. Also see ref 7.
51. In the intramolecular reaction (Scheme 2), an aminyl radical pathway cannot be discarded, while we confirmed the negligible effects of TEMPO and galvinoxyl (the SI).