Versatile catalysts for the Suzuki cross-coupling of arylboronic acids with aryl and vinyl halides and triflates under mild conditions

Journal of the American Chemical Society

Volumn 122, Issue 17, 2000, Pages 4020-4028

  Littke, Adam F ^a   Dai, Chaoyang ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BORONIC ACID DERIVATIVE; HALIDE; TRIFLUOROMETHANESULFONIC ACID; VINYL DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMOSENSITIVITY; COMPLEX FORMATION; REACTION ANALYSIS; SYNTHESIS;

EID: 0034600318     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0002058     Document Type: Article

References (136)

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32. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
33. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
34. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
35. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
36. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
37. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
38. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
39. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197-201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
40. 3 in palladium-catalyzed couplings of aryl chlorides, see: (a) Amination: Nishiyama, M.; Yamamoto, T.; Koie, Y.; Tetrahedron Lett. 1998, 39, 617-620. Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.; Shaughnessy, K. H.; Alcazar-Roman, L. M. J. Org. Chem. 1999, 64, 5575-5580. (b) Heck reaction: Littke, A. F.; Fu. G. C. J. Org. Chem. 1999, 64, 10-11. Shaughnessy, K. H.; Kim, P.; Hartwig, J. F. J. Am. Chem, Soc. 1999, 121, 2123-2132. (c) Reaction of ketone enolates: Kawatsura, M.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 1473-1478. (d) Reaction of alkoxides: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225. Watanabe, M.; Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1999, 40, 8837-8840. (e) Amidocarbonylation: Kim, J. S.; Sen, A. J. Mol. Catal. A 1999, 143, 197- 201. (f) Stille reaction: Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 1999, 38, 2411-2413.
41. Zhang, C.; Huang, J.; Trudell, M. L.; Nolan, S. P. J. Org. Chem. 1999, 64, 3804-3805.
42. (a) Herrmann, W. A.; Reisinger, C-P.; Spiegler, M. J. Organomet. Chem. 1998, 557, 93-96.
43. (b) Weskamp, T.; Bohm, V. P. W.; Herrmann, W. A. J. Organomet. Chem. 1999, 585, 348-352.
44. See also: Firooznia, F.; Gude, C.; Chan, K.; Satoh, Y. Tetrahedron Lett. 1998, 39, 3985-3988.
45. See also: Kocovsky, P.; Vyskocil, S.; Cisarova, I.; Sejbal, J.; Tislerova, I.; Smrcina, M.; Lloyd-Jones, G. C.; Stephen, S. C.; Butts, C. P.; Murray, M.; Langer, V. J. Am. Chem. Soc. 1999, 121, 7714-7715.
46. For an application of this method, see: Firooznia, F.; Gude, C.; Chan, K.; Marcopulos, N.; Satoh, Y. Tetrahedron Lett. 1999, 40, 213-216.
47. See footnote 9 of ref 6.
48. (a) Ichikawa, J.; Moriya, T.; Sonoda, T.; Kobayashi, H. Chem. Lett. 1991, 961-964.
49. (b) Wright, S. W.; Hageman, D. L.; McClure, L. D. J. Org. Chem. 1994, 59, 6095-6097.
50. For an explanation of this observation, see the section that describes mechanistic work on Suzuki cross-couplings of aryl chlorides and aryl bromides (vide infra).
51. For our original optimization work, see ref 6.
52. 3, no coupling between 4′-chloroacetophenone and o-tolylboronic acid is observed at room temperature (cf. Table 1, entry 1).
53. Under these nonaqueous conditions, hydrolytic cleavage of the B-C bond is not a concern. For discussions of this issue, see ref 1.
54. Dioxane is also a suitable solvent.
55. Cross-coupling can also be effected at 0°C, although the reaction is slower.
56. 3:Pd is employed.
57. The need for a higher temperature for the reaction of cyclopentylboronic acid may be due to the slower rate of transmetalation by alkylboron compounds, relative to arylboron compounds. For example, see ref 21b.
58. (a) Campi, E. M.; Jackson, W. R.; Marcuccio, S. M.; Naeslund, C. G. M. J. Chem. Soc., Chem. Commun. 1994, 2395.
59. (b) Anderson, J. C.; Namli, H.; Roberts, C. A. Tetrahedron 1997, 53, 15123-15134.
60. (c) Johnson, C. R.; Johns, B. A. Synlett 1997, 1406-1408.
61. (d) Bumagin, N. A.; Bykov, V. V. Tetrahedron 1997, 53, 14437-14450.
62. (e) Albisson, D. A.; Bedford, R. B.; Lawrence, S. E.; Scully, P. N. Chem. Commun. 1998, 2095-2096.
63. (f) Uozumi, Y.; Danjo, H.; Hayashi, T. J. Org. Chem. 1999, 64, 3384-3388.
64. (g) Kamatani, A.; Overman, L. E. J. Org. Chem. 1999, 64, 8743-8744.
65. (h) Bussolari, J. C.; Rehborn, D. C. Org. Lett. 1999, 1, 965-967.
66. 3 as the phosphine.
67. Because these reaction mixtures are heterogeneous, the relative times that are necessary for the cross-couplings to proceed to completion may not reflect the relative intrinsic reactivities of the substrates.
68. (a) Metal-Catalyzed Cross-Coupling Reactions; Diederich, F., Stang, P. J., Eds.; Wiley-VCH: New York, 1998.
69. (b) Tsuji, J. Palladium Reagents and Catalysis; Wiley: New York, 1995.
70. (c) Farina, V. In Comprehensive Organometallic Chemistry 2; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: New York, 1995; Vol. 12, Chapter 3.4.
71. (d) Reference 1.
72. 4NF as an additive was also effective.
73. For further discussion, see the section that describes mechanistic work on Suzuki cross-couplings of aryl iodides (vide infra).
74. For reviews of the chemistry of vinyl and aryl triflates, see: (a) Ritter, K. Synthesis 1993, 735-762. (b) Stang, P. J.; Hanack, M.; Subrmanian, L. R. Synthesis 1982, 85-126.
75. For reviews of the chemistry of vinyl and aryl triflates, see: (a) Ritter, K. Synthesis 1993, 735-762. (b) Stang, P. J.; Hanack, M.; Subrmanian, L. R. Synthesis 1982, 85-126.
76. Oh-e, T.; Miyaura, N.; Suzuki. A. J. Org. Chem. 1993, 58, 2201-2208.
77. (a) For a report of a room-temperature cross-coupling of phenyl inflate with 9-octyl-9-BBN, see ref 37.
78. (b) For a report of a room-temperature cross-coupling of a vinylboronic acid with an activated aryl inflate (bearing a 4-(ethoxycarbonyl) group), see: Torrado, A.; Lopez, S.; Alvarez, R.; de Lera, A. R. Synthesis 1995, 285-293.
79. 3: 182°. For an extensive compilation of phosphine cone angles, see: Rahman, M. M.; Liu, H.-Y.; Eriks, K.; Prock, A.; Giering, W. P. Organometallics 1989, 8, 1-7.
80. 2 are also effective cross-coupling catalysts.
81. Under other, more vigorous conditions for Suzuki reactions, hydrolysis of the triflate is sometimes observed. For example, see: (a) Coudret, C.; Mazenc, V. Tetrahedron Lett. 1997, 38, 5293-5296. (b) Fu, J.-m.; Snieckus, V. Tetrahedron Lett. 1990, 31, 1665-1668.
82. Under other, more vigorous conditions for Suzuki reactions, hydrolysis of the triflate is sometimes observed. For example, see: (a) Coudret, C.; Mazenc, V. Tetrahedron Lett. 1997, 38, 5293-5296. (b) Fu, J.-m.; Snieckus, V. Tetrahedron Lett. 1990, 31, 1665-1668.
83. (a) For the cross-coupling of a heteroaryl chloride, see refs 10d and 10h.
84. (b) For a nickel-catalyzed cross-coupling, see: Galland, J.-C.; Savignac, M.; Genet, J.-P. Tetrahedron Lett. 1999, 40, 2323-2326.
85. Thus far, our attempts to efficiently produce biaryls that bear four ortho substituents have been unsuccessful.
86. For example, see: (a) Kawada, K.; Arimura, A.; Tsuri, T.; Fuji, M.; Komurasaki, T.; Yonezawa, S.; Kugimiya, A.; Haga, N.; Mitsumori, S.; Inagaki, M.; Nakatani, T.; Tamura, Y.; Takechi, S.; Taishi, T.; Kishino, J.; Ohtani, M. Angew. Chem., Int. Ed. 1998, 37, 973-975. (b) Hird, M.; Gray, G. W.; Toyne, K. J. Mol. Cryst. Liq. Cryst. 1991, 206, 187-204.
87. For example, see: (a) Kawada, K.; Arimura, A.; Tsuri, T.; Fuji, M.; Komurasaki, T.; Yonezawa, S.; Kugimiya, A.; Haga, N.; Mitsumori, S.; Inagaki, M.; Nakatani, T.; Tamura, Y.; Takechi, S.; Taishi, T.; Kishino, J.; Ohtani, M. Angew. Chem., Int. Ed. 1998, 37, 973-975. (b) Hird, M.; Gray, G. W.; Toyne, K. J. Mol. Cryst. Liq. Cryst. 1991, 206, 187-204.
88. 4 furnishes high selectivity, see ref 37 (in contrast with ref 41b).
89. 4 (ref 37).
90. 3. low selectivity is observed.
91. 3.
92. 3 leads to predominant Suzuki cross-coupling of the aryl triflate, rather than the aryl chloride.
93. For leading references, see: Goubet, D.; Meric, P.; Dormoy, J.-R.; Moreau, P. J. Org. Chem. 1999, 64, 4516-4518.
94. (a) Beller, M.; Fischer, H.; Herrmann, W. A.; Ofele, K.; Brossmer, C. Angew. Chem., Int. Ed. Engl. 1995, 34, 1848-1849.
95. (b) References 12b and 12c.
96. 3.
97. To the best of our knowledge, 950 is the highest turnover number that has been reported for a room-temperature Suzuki coupling of an aryl bromide (with an activated aryl bromide, 4-bromoacetophenone; ref 30e).
98. Armstrong, R. W.; Beau, J.-M.; Cheon, S. H.; Christ, W. J.; Fujioka, H.; Ham, W.-H.; Hawkins L. D.; Jin, H.; Kang, S. H.; Kishi, Y.; Martinelli, M. J.; McWhorter, W. W.; Mizuno, M.; Nakata, M.; Stutz, A. E.; Talamas, F. X.; Taniguchi, M.; Tino, J. A.; Ueda, K.; Uenishi, J.-i.; White, J. B.; Yonaga, M. J. Am. Chem. Soc. 1989, 111, 7525-7530.
99. Evans, D. A.; Ng, H. P.; Rieger, D. L. J. Am. Chem. Soc. 1993, 115, 11446-11459.
100. Su, K.-S.; Meng, D.; Bertinato, P.; Balog, A.; Sorensen, E. J.; Danishefsky, S. J.; Zheng, Y.-H.; Chou, T.-C.; He, L.; Horwitz, S. B. Angew. Chem., Int. Ed. Engl. 1997, 36, 757-759.
101. (a) Satoh, N.; Ishiyama, T.; Miyaura, N.; Suzuki, A. Bull. Chem. Soc. Jpn. 1987, 60, 3471-3473.
102. (b) Boland, G. M.; Donnelly, D. M. X.; Finet, J.-P.; Rea, M. D. J. Chem. Soc., Perkin Trans. I 1996, 2591-2597.
103. (a) Roush, W. R.; Moriarty, K. J.; Brown, B. B. Tetrahedron Lett. 1990, 31, 6509-6512. Roush, W. R.; Koyama, K.; Curtin, M. L.; Moriarty, K. J. J. Am. Chem. Soc. 1996, 118, 7502-7512.
104. (a) Roush, W. R.; Moriarty, K. J.; Brown, B. B. Tetrahedron Lett. 1990, 31, 6509-6512. Roush, W. R.; Koyama, K.; Curtin, M. L.; Moriarty, K. J. J. Am. Chem. Soc. 1996, 118, 7502-7512.
105. (b) Baldwin, J. E.; Chesworth, R.; Parker, J. S.; Russell, A. T. Tetrahedron Lett. 1995, 36, 9551-9554.
106. (c) Johnson, C. R.; Johns, B. A. Tetrahedron Lett. 1997, 38, 7977-7980. Johns, B. A.; Pan, Y. T.; Elbein, A. D.; Johnson, C. R. J. Am. Chem. Soc. 1997, 119, 4856-4865.
107. (c) Johnson, C. R.; Johns, B. A. Tetrahedron Lett. 1997, 38, 7977-7980. Johns, B. A.; Pan, Y. T.; Elbein, A. D.; Johnson, C. R. J. Am. Chem. Soc. 1997, 119, 4856-4865.
108. (d) Koch, F.; Heitz, W. Macromol. Chem. Phys. 1997, 198, 1531-1544.
109. (e) Uenishi, J.; Kawahama, R.; Yonemitsu, O.; Tsuji, J. J. Org. Chem. 1998, 63, 8965-8975.
110. 3 are less effective catalyst components.
111. The vinyl triflate in entries 8 and 9 has proved to be a challenging substrate in other cross-coupling processes. For example, see: Busacca, C. A.; Eriksson, M. C.; Fiaschi, R. Tetrahedron Lett. 1999, 40, 3101-3104.
112. (a) Unactivated vinyl inflates: Sasaki, M.; Fuwa, H.; Inoue, M.; Tachibana, K. Tetrahedron Lett. 1998, 39, 9027-9030. Brosius, A. D.; Overman, L. E.; Schwink, L. J. Am. Chem. Soc. 1999, 121, 700-709. Reference 30g.
113. (a) Unactivated vinyl inflates: Sasaki, M.; Fuwa, H.; Inoue, M.; Tachibana, K. Tetrahedron Lett. 1998, 39, 9027-9030. Brosius, A. D.; Overman, L. E.; Schwink, L. J. Am. Chem. Soc. 1999, 121, 700-709. Reference 30g.
114. (b) Activated vinyl Inflates: Yasuda, N.; Xavier, L.; Rieger, D. L.; Li, Y.; DeCamp, A. E.; Dolling, U.-H. Tetrahedron Lett. 1993, 34, 3211-3214. Fu, J.-m.; Chen, Y.; Catelhano, A. L. Synlett 1998, 1408- 1410.
115. (b) Activated vinyl Inflates: Yasuda, N.; Xavier, L.; Rieger, D. L.; Li, Y.; DeCamp, A. E.; Dolling, U.-H. Tetrahedron Lett. 1993, 34, 3211-3214. Fu, J.-m.; Chen, Y.; Catelhano, A. L. Synlett 1998, 1408-1410.
116. 4 more rapidly than do aryl triflates: Farina, V.; Krishnan, B.; Marshall, D. R.; Roth, G. P. J. Org. Chem. 1993, 58, 5434-5444.
117. (a) Otsuka, S.; Yoshida, T.; Matsumoto, M.; Nakatsu, K. J. Am. Chem. Soc. 1976, 98, 5850-5858.
118. (b) Yoshida, T.; Otsuka, S. J. Am. Chem. Soc. 1977, 99, 2134-2140.
119. 2.
120. (a) For a closely related study, see: Paul, F.; Patt, J.; Hartwig, J. F. Organometallics 1995, 14, 3030-3039.
121. 3: Amatore, C.; Jutand, A.; Khalil, F.; M'Barki, M. A.; Mottier, L. Organometallics 1993, 12, 3168-3178.
122. A very small singlet at δ 90.7 is observed at the beginning of the reaction, but it disappears as the reaction progresses.
123. 3:Pd ratio of 2:1 is employed.
124. 3 is not an effective catalyst for the cross-coupling of aryl chlorides.
125. 3 is available as a solution in a Sure-Seal bottle from Strem Chemicals.
126. 3-based catalysts, a palladium bisphosphine adduct is usually invoked (ref 1).
127. 3 ligand, see: Krause, J.; Cestaric, G.; Haack, K.-J.; Seevogel, K.; Storm, W.; Pörschke, K.-R. J. Am. Chem. Soc. 1999, 121, 9807-9823.
128. 3.
129. 3 in the absence of phenylboronic acid and KF.
130. 2 appears at δ 85.6.
131. For related conclusions regarding Suzuki reactions catalyzed by PPh3-based palladium complexes, see: Smith, G. B.; Dezeny, G. C.; Hughes, D. L.; King, A. O.; Verhoeven, T. R. J. Org. Chem. 1994, 59, 8151-8156.
132. Vedejs, E.; Chapman, R. W.; Fields, S. C.; Lin, S.; Schrimpf, M. R. J. Org. Chem. 1995, 60, 3020-3027.
133. 3 has been shown to serve as an arylating agent in palladium-catalyzed cross-couplings with arenediazonium salts: Darses, S.; Genet, J.-P.; Brayer, J.-L.; Demoute, J.-P. Tetrahedron Lett. 1997, 38, 4393-4396. Darses, S.; Michaud, G.; Genet, J.-P. Eur. J. Org. Chem. 1999, 1875- 1883.
134. 3 has been shown to serve as an arylating agent in palladium- catalyzed cross-couplings with arenediazonium salts: Darses, S.; Genet, J.-P.; Brayer, J.-L.; Demoute, J.-P. Tetrahedron Lett. 1997, 38, 4393-4396. Darses, S.; Michaud, G.; Genet, J.-P. Eur. J. Org. Chem. 1999, 1875-1883.
135. Hartwig has noted that an effective catalyst for palladium-catalyzed C-O bond formation can be formed from a 1:2 mixture of phosphine and palladium: Mann, G.; Incarvito, C.; Rheingold, A. L.; Hartwig, J. F. J. Am. Chem. Soc. 1999, 121, 3224-3225.
136. Under low-phosphine conditions above room temperature, there appears to be a greater tendency to form insoluble Pd(0).