Copper-Catalyzed Enantioselective Allyl–Allyl Coupling between Allylic Boronates and Phosphates with a Phenol/N-Heterocyclic Carbene Chiral Ligand

Angewandte Chemie - International Edition

Volumn 55, Issue 36, 2016, Pages 10816-10820

  Yasuda, Yuto ^a   Ohmiya, Hirohisa ^a   Sawamura, Masaya ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

allylic compounds; asymmetric catalysis; boron; copper; synthetic methods

Indexed keywords

BORON; CATALYSIS; COPPER; ENANTIOSELECTIVITY; ORGANIC COMPOUNDS; PHOSPHATES;

ALLYLIC COMPOUNDS; ALLYLIC PHOSPHATES; ASYMMETRIC CATALYSIS; CHIRAL N-HETEROCYCLIC CARBENES; COPPER CATALYZED; HIGH ENANTIOSELECTIVITY; STEREOGENIC CENTERS; SYNTHETIC METHODS;

LIGANDS;

EID: 84983559877     PISSN: 14337851     EISSN: 15213773     Source Type: Journal    
DOI: 10.1002/anie.201605125     Document Type: Article

References (45)

1. For selected papers, see:
2. B. M. Trost, E. Keinan, Tetrahedron Lett. 1980, 21, 2595;
3. J. Godschalx, J. K. Stille, Tetrahedron Lett. 1980, 21, 2599;
4. H. Nakamura, M. Bao, Y. Yamamoto, Angew. Chem. Int. Ed. 2001, 40, 3208;
5. Angew. Chem. 2001, 113, 3308;
6. A. S. E. Karlström, J.-E. Bäckvall, Chem. Eur. J. 2001, 7, 1981;
7. A. Jimeńez-Aquino, E. F. Flegeau, U. Schneider, S. Kobayashi, Chem. Commun. 2011, 47, 9456;
8. Q. Yuan, K. Yao, D. Liu, W. Zhang, Chem. Commun. 2015, 51, 11834.
9. E. Breitmaier, Terpenes: Flavors, Fragrances, Pharmaca, Pheromones, Wiley-VCH, Weinheim, 2006. See also Refs. [3–6] and references therein.
10. P. Zhang, L. A. Brozek, J. P. Morken, J. Am. Chem. Soc. 2010, 132, 10686;
11. P. Zhang, H. Le, R. E. Kyne, J. P. Morken, J. Am. Chem. Soc. 2011, 133, 9716;
12. L. A. Brozek, M. J. Ardolino, J. P. Morken, J. Am. Chem. Soc. 2011, 133, 16778;
13. M. J. Ardolino, J. P. Morken, J. Am. Chem. Soc. 2014, 136, 7092;
14. M. J. Ardolino, J. P. Morken, Tetrahedron 2015, 71, 6409.
15. V. Hornillos, M. Pérez, M. Fañanás-Mastral, B. L. Feringa, J. Am. Chem. Soc. 2013, 135, 2140.
16. J. Y. Hamilton, N. Hauser, D. Sarlah, E. M. Carreira, Angew. Chem. Int. Ed. 2014, 53, 10759;
17. Angew. Chem. 2014, 126, 10935.
18. For the synthesis of chiral 1,5-diene derivatives through copper-catalyzed enantioselective coupling with diboron, allene, and allylic phosphate, see: F. Meng, K. P. McGrath, A. H. Hoveyda, Nature 2014, 513, 367.
19. For reviews on copper-catalyzed allylic substitutions, see:
20. A. Alexakis, J. E. Bäckvall, N. Krause, O. Pàmies, M. Diéguez, Chem. Rev. 2008, 108, 2796;
21. S. R. Harutyunyan, T. den Hartog, K. Geurts, A. J. Minnaard, B. L. Feringa, Chem. Rev. 2008, 108, 2824;
22. R. Shintani, Synthesis 2016, 48, 1087.
23. For copper-catalyzed enantioselective allylic substitutions using organoboron reagents and oxygen-functionalized NHC chiral ligands, see:
24. R. Shintani, K. Takatsu, M. Takeda, T. Hayashi, Angew. Chem. Int. Ed. 2011, 50, 8656;
25. Angew. Chem. 2011, 123, 8815;
26. F. Gao, J. L. Carr, A. H. Hoveyda, Angew. Chem. Int. Ed. 2012, 51, 6613;
27. Angew. Chem. 2012, 124, 6717;
28. B. Jung, A. H. Hoveyda, J. Am. Chem. Soc. 2012, 134, 1490;
29. Y. Shi, B. Jung, S. Torker, A. H. Hoveyda, J. Am. Chem. Soc. 2015, 137, 8948. See also Ref. [7c].
30. A. Harada, Y. Makida, T. Sato, H. Ohmiya, M. Sawamura, J. Am. Chem. Soc. 2014, 136, 13932. See also:
31. H. Ohmiya, H. Zhang, S. Shibata, A. Harada, M. Sawamura, Angew. Chem. Int. Ed. 2016, 55, 4777;
32. Angew. Chem. 2016, 128, 4855.
33. Y. Shido, M. Yoshida, M. Tanabe, H. Ohmiya, M. Sawamura, J. Am. Chem. Soc. 2012, 134, 18573;
34. K. Hojoh, Y. Shido, H. Ohmiya, M. Sawamura, Angew. Chem. Int. Ed. 2014, 53, 4954;
35. Angew. Chem. 2014, 126, 5054. See also:
36. H. Ohmiya, U. Yokobori, Y. Makida, M. Sawamura, J. Am. Chem. Soc. 2010, 132, 2895;
37. K. Nagao, U. Yokobori, Y. Makida, H. Ohmiya, M. Sawamura, J. Am. Chem. Soc. 2012, 134, 8982.
38. The use of allyl-9-BBN reagent instead of 1 a under the reaction conditions used for entry 12 in Table 1, resulted in decreases in both enantioselectivity (87 % ee) and product yield (30 %) but with the exclusive regioselectivity (γ/α>99:1) unchanged.
39. M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953.
40. The absolute configurations of 3 ae and 3 ah were determined by comparison of the specific rotations with the values reported previously. See Ref. [3a]. The absolute configuration of 3 ar was determined by the Mosher's NMR spectroscopic method. Absolute configurations of the other products were assigned by consideration of the stereochemical pathway. See the Supporting Information for details.
41. The linear α-substitution product was the E isomer.
42. −. Our proposed mechanism is in accord with the Nakamura's mechanism in that the reaction proceeds through oxidative addition of a cuprate to form the (γ-σ-enyl)copper(III) species followed by reductive elimination. However, the coordination number of Cu in the allylcopper(III) complex is different by virtue of bidentate coordination of the anionic phenol/NHC chiral ligand (L). The strongly electron-donating NHC coordination should render the π–en coordination weaker, thus making the allylic 1,3-copper migration in the allylcopper(III) complex more feasible. See:
43. N. Yoshikai, S.-L. Zhang, E. Nakamura, J. Am. Chem. Soc. 2008, 130, 1286. For the effect of a σ-donor ligand, see:
44. M. Yamanaka, S. Kato, E. Nakamura, J. Am. Chem. Soc. 2004, 126, 6287.
45. 11B NMR spectroscopy. See the Supporting Information for details.