Scope and mechanism of the iridium-catalyzed cleavage of alkyl ethers with triethylsilane

Journal of the American Chemical Society

Volumn 130, Issue 51, 2008, Pages 17509-17518

  Yang, Jian ^a   White, Peter S ^a   Brookhart, Maurice ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACTIVE CATALYST; ALKYL ETHERS; CATALYST RESTING STATE; CATALYTIC CYCLES; CATALYTIC REDUCTION; DIETHYL ETHERS; DIHYDRIDE; HYDRIDE REDUCTION; LIMITING STEP; MECHANISTIC STUDIES; OXONIUM ION; PINCER COMPLEXES; RAPID EQUILIBRIUM; REACTION MIXTURE; RELATIVE RATES; ROOM TEMPERATURE; TRIETHYLSILANE;

ACETONE; ALKYLATION; CATALYSIS; CATALYSTS; IONS; IRIDIUM; IRIDIUM COMPOUNDS; ORGANIC COMPOUNDS; SILANES;

ETHERS;

[2,6 [OP(TBU)2]2C6H3 IRIDIUM(H) (ACETONE)] [B(C6F5)4]; [2,6 [OP(TBU)2]2C6H3 IRIDIUM(H)2; [TRIETHYLSILANOXONIUMEDIETHYL] [B(C6F5)4]; ALKYL ETHER; ANISOLE; DIETHYL(TRIETHYLSILYL)OXONIUM; ETHER; IRIDIUM COMPLEX; SILANE DERIVATIVE; TRIETHYLSILANE; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL BOND; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; EQUILIBRIUM CONSTANT; MOLECULAR MECHANICS; ROOM TEMPERATURE; SYNTHESIS;

EID: 67749133709     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja806419h     Document Type: Article

References (65)

1. (a) Kubas, G. J. Metal Dihydrogen and o-Bond Complexes: Kluwer Academic/Plenum Publishers: New York, 2001.
2. (b) Kubas, G. J. Adp. hwrg. Chem. 2004, 56, 127.
3. (c) Kubas. G. J. Chem. Rev. 2007, 107, 4152.
4. (a) Bullock, R. M. Chem. Eur. J. 2004, 10, 2366.
5. (b) Bullock, R. M. In Handbook of Homogeneous Hvdrogenation de Vries, J. G., Elsevier. C. J., Eds.; Wiley-VCH: Weinheim, 2007; Chapter 7.
6. (a) Guan, H.; Iimura. M.; Magee, M. P.; Norton, J. R.; Zhu, G.1. Am. Chem. Soc. 2005, 127, 7805.
7. (b) Magee, M. P.; Norton, J. R. J.Am. Chem. Soc. 2001, 123, 1778.
8. (c) Guan, H.; Saddoughi, S. A.; Shaw, A. P.; Norton, J. R. OreanometalUcs 2005, 24, 6358.
9. (d) Guan, H.; Iimura. M.; Magee. M. P.; Norton, J. R.; Janak, K. E. OreanometalUcs 2003, 22, 4084.
10. (a) Stephan, D. W. Org. Biomol. Chem. 2008, 6, 1535.
11. (b) Kenward, A. L.; Piers. W. E. Angew. Chem., Int. Ed. 2008, 47, 38.
12. (c) Welch, G. C; Stephan, D. W. J Am. Chem. Soc. 2007, 129, 1880.
13. (d) Spies, P.; Erker, G.; Kehr, G.; Bergander, K.; Frohlich, R.; Grimme, S.: Stephan, D. W. Chem. Comrnun. 2007, 5072.
14. (e) Chase, P. A.; Welch, G. C; Jurca, T.; Stephan, D. W. Angew. Chem., Int. Ed. 2007, 49, 8050.
15. (f) Chase. P. A.; Jurca. T.; Stephan, D. W. Chem. Comrnun. 2008, 1701.
16. (g) Welch, G. C; Cabrera. L.; Chase, P. A.; Hollink, E.; Masuda, J. D.; Wei. P.; Stephan. D. W. Dalton Trans. 2007, 3407.
17. (h) Welch, G. C; Juan. R. R. S.; Masuda. J. D.; Stephan, D. W. Science 2006, 314, 1124.
18. (a) Piers. W. E. Adv. Organomet. Chem. 2005, 52, 1.
19. (b) Parks, D. J.; Blackwell, J. M.; Piers, W. E. J. Org. Chem. 2000, 65, 3090.
20. (c) Parks, D. J.; Piers, W. E. J.Am. Chem. Soc. 1996, 118, 9440.
21. (d) Blackwell. J. M.; Sonmor, E. R.; Scoccitti, T.; Piers, W. E. (Org. Lett. 2000, 2, 3921.
22. (e) Blackwell. J. M.; Morrison. D. J.; Piers, W. E. Tetrahedron 2002, 58, 8247.
23. (t) Rubin. M.; Schwier. T.: Gevorgvan, V. J.Org. Chem. 2002, 67, 1936.
24. (a) Du, G.; Fanwick, P. E.; Abu-Omar. M. M. J.Am. Chem. Soc. 2007, 129, 5180.
25. (b) Dioumaev. V. K.; Bullock. R. M. Nature 2003, 424. 530.
26. It is known that hydrosilanes are able to reduce alkyl ethers in the presence of stoichiometric (or excess) amounts of Lewis acids: (a) Adlington, M. G.; Orfanopoulos, M.; Fry, J. L. Tetrahedron Lett. 1976, 2955.
27. (b) Fry, J. L.; Orfanopoulos, M.; Adlington, M. G.; Dittman, W. R.; Silverman, S. B. J.Org. Chem. 1978,43, 374.
28. (c) Orfanopoulos, M.; Smonou. I. Synth. Commun. 1988, 18, 833.
29. (d) Larsen. J. W.; Chang. L. W. J.Org. Chem. 1979, 44, 1168.
30. (e) Yato, M.; Ishida, A. Heterocycles 1995, 41, 17.
31. (f) Smonou, 1. Synth. Commun. 1994, 24, 1999.
32. 3SiH:
33. (h) Rubenbauer. P.; Bach, T. Tetrahedron Lett. 2008, 49, 1305.
34. (a) Gevorgyan, V.; Rubin, M.; Benson, S.; Liu, J.-X.; Yamamoto, Y. J.Org. Chem. 2000, 65, 6179.
35. (b) Gevorgyan, V.; Liu, J.-X.; Rubin, M.; Benson. S.: Yamamoto, Y. Tetrahedron Lett. 1999, 40, 8919.
36. Also see: (c) Blackwell, J. M.; Foster, K. L.; Beck, V. H.; Piers, W. E. J. Org. Chem. 1999, 64, 4887.
37. 3SiH reduction of certain classes of primary and secondary alcohols: (d) Ferreri, C; Costantino, C; Chatgilialoglu, C; Boukherroub. R.; Manuel, G. J. Organomet. Chem. 1998, 554, 135.
38. (a) Nimmagadda, R. D.; McRae, C. Tetrahedron Lett. 2006, 47, 5755.
39. 3SiH: (b) Gevorgyan, V.; Rubin, M.; Liu, J.-X.; Yamamoto, Y. /. Org. Chem. 2001,' 66, 1612.
40. (c) Bajracharya, G. B.; Nogami, T.; Jin, T.; Matsuda, K.; Gevorgyan, V.; Yamamoto, Y. Synthesis 2004, 308.
41. With polymethylhydrosiloxane as reductant: (d) Chandrasekhar, S.; Reddv. C. R.; Babu. B. N. /. Org. Chem. 2002, 67, 9080.
42. Chojnowski, J.; Rubinsztajn, S.; Cella, J. A.; Fortuniak, W.; Cypryk, M.; Kurjata, J.; Kazmierski, K. Organometallics 2005, 24, 6077.
43. Yang, J.; Brookhart, M. J. Am. Chem. Soc. 2007, 129, 12656.
44. Yang, J.; White, P. S.; Schauer. C. K.; Brookhart, M. Angew. Chem., Int. Ed. 2008, 47, 4141.
45. Active catalyst species were not very soluble in neat diethyl ether and triethylsilane; therefore, the solvent-free reduction of diethyl ether was carried out at an elevated reaction temperature (65 °C); see Experimental Section for details.
46. Goettker-Schnetmann, I.; White, P.; Brookhart, M. Orsanometallics 2004, 23, 1766.
47. (a) Kira, M.; Hino, T.; Sakurai, H. J. Am. Chem. Soc. 1992, 114, 6697.
48. (b) Scharrer. E.; Chang, S.; Brookhart, M. Organometallics 1995, 14, 5686.
49. (a) Lambert, J. B.; Zhao, Y.; Wu, H. J. Org. Chem. 1999, 64, 2729.
50. (b) Lambert. J. B.; Zhang, S.; Ciro. S. M. Organometallics 1994, 13, 2430.
51. (c) Lambert. J. B.; Kania. L.; Zhang. S. Chem. Rev. 1995, 95, 1191.
52. (d) Reed, C. A. Acc. Chem. Res. 1998, 31, 325.
53. (e) Lambert, J. B.; Zhang, S.; Stern, C. L.; Huffman, J. C. Science 1993, 260, 1917.
54. (f) Corey, J. Y. J. Am. Chem. Soc. 1975, 97, 3237.
55. (g) Müller, T. Adv. Organomet. Chem. 2005, 53, 155.
56. +ions (E = P, As) and also by independent synthesis: (a) Driess, M.; Barmever. R.; Monsé C; Merz, K. Angew, Chem., Int. Ed. 2001, 40, 2308.
57. + ion: Xie, Z.; Bau, R.: Reed. C. A. Chem. Comrnun. 1994, 2519.
58. (c) Olah, G. A.; Li. X.-Y.; Wang. Q.; Rasul, G.; Prakash. G. K. S. J.Am. Chem. Soc. 1995, 117. 8962.
59. 3SiOEt.
60. (a) Scott. V. J.; gelenligil-getin. R.; Ozerov. O. V. J.Am. Chem. Soc. 2005, 127, 2852.
61. 3SiH.
62. 5C1 according to procedures analogous to that for 7; see Experimental Section for details.
63. (a) lshihara, K. In Lewis Acids in Organic Synthesis; Yamamoto, H., Ed.: Wiley-VCH: Weinheim, 2000; Vol. 1, p 91.
64. (b) Kocienski. P. J. Protecting Groups; Thieme: Stuttgart. New York, 1994; p 42.
65. (a) Alaimo, P. J.; Peters. D. W.; Arnold, J.; Bergman. R. G. J.Chem. Educ. 2001, 78, 64. (b) Pangborn, A. B.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J. Organometallics 1996, 15, 1518.