Use of molecular oxygen as a reoxidant in the synthesis of 2-substituted benzothiazoles via palladium-catalyzed C-H functionalization/intramolecular C-S bond formation

Advanced Synthesis and Catalysis

Volumn 352, Issue 14-15, 2010, Pages 2643-2655

  Inamoto, Kiyofumi ^a   Hasegawa, Chisa ^a   Kawasaki, Junpei ^a   Hiroya, Kou ^a   Doi, Takayuki ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

benzothiazoles; C H functionalization; C S bond formation; cyclization; molecular oxygen; palladium

Indexed keywords

EID: 78349264903     PISSN: 16154150     EISSN: 16154169     Source Type: Journal    
DOI: 10.1002/adsc.201000604     Document Type: Article

References (162)

1. For recent reviews on transition metal-catalyzed C-H functionalization, see
2. L. Ackermann, Chem. Commun. 2010, 46, 4866 - 4877
3. T. W. Lyons, M. S. Sanford, Chem. Rev. 2010, 110, 1147 - 1169
4. J. A. Ashenhurst, Chem. Soc. Rev. 2010, 39, 540 - 548
5. C.-L. Sun, B.-J. Li, Z.-J. Shi, Chem. Commun. 2010, 46, 677 - 685
6. L. Ackermann, R. Vincente, A. R. Kapdi, Angew. Chem. 2009, 121, 9976 - 10011
7. Angew. Chem. Int. Ed. 2009, 48, 9792 - 9826
8. X. Chen, K. M. Engle, D.-H. Wang, J.-Q. Yu, Angew. Chem. 2009, 121, 5196 - 5217
9. Angew. Chem. Int. Ed. 2009, 48, 5094 - 5115
10. O. Daugulis, H.-Q. Do, D. Shabashov, Acc. Chem. Res. 2009, 42, 1074 - 1086
11. F. Collet, R. H. Dodd, P. Dauban, Chem. Commun. 2009, 5061 - 5074
12. P. Thansandote, M. Lautens, Chem. Eur. J. 2009, 15, 5874 - 5883
13. M. Zhang, Adv. Synth. Catal. 2009, 351, 2243 - 2270
14. C.-J. Li, Acc. Chem. Res. 2009, 42, 335 - 344
15. G. P. McGlacken, L. M. Bateman, Chem. Soc. Rev. 2009, 38, 2447 - 2464
16. H. M. L. Davies, J. R. Manning, Nature 2008, 451, 417 - 424
17. B.-J. Li, S.-D. Yang, Z.-J. Shi, Synlett 2008, 949 - 957
18. F. Kakiuchi, T. Kochi, Synthesis 2008, 3013 - 3039
19. M. Rubin, M. Rubina, V. Gevorgyan, Chem. Rev. 2007, 107, 3117 - 3179
20. L.-C. Campeau, D. R. Stuart, K. Fagnou, Aldrichimica Acta 2007, 40, 35 - 41.
21. Compared to C-C, C-O, and C-X bond formation, only a few reports exist about C-N bond formation via palladium-catalyzed C-H functionalization, see
22. K. Inamoto, T. Saito, K. Hiroya, T. Doi, J. Org. Chem. 2010, 75, 3900 - 3903
23. Y. Tan, J. F. Hartwig, J. Am. Chem. Soc. 2010, 132, 3676 - 3677
24. Z. Ke, T. R. Cundari, Organometallics 2010, 29, 821 - 834
25. T.-S. Mei, X. Wang, J.-Q. Yu, J. Am. Chem. Soc. 2009, 131, 10806 - 10807
26. J. J. Neumann, S. Rakshit, T. Dröge, F. Glorius, Angew. Chem. 2009, 121, 7024 - 7027
27. Angew. Chem. Int. Ed. 2009, 48, 6892 - 6895
28. T. Miura, Y. Ito, M. Murakami, Chem. Lett. 2009, 38, 328 - 329
29. J. A. Jordan-Hore, C. C. C. Johansson, M. Gulias, E. M. Beck, M. J. Gaunt, J. Am. Chem. Soc. 2008, 130, 16184 - 16186
30. M. Wasa, J.-Q. Yu, J. Am. Chem. Soc. 2008, 130, 14058 - 14059
31. W. C. P. Tsang, R. H. Munday, G. Brasche, N. Zheng, S. L. Buchwald, J. Org. Chem. 2008, 73, 7603 - 7610
32. B.-J. Li, S.-L. Tian, Z. Fang, Z.-J. Shi, Angew. Chem. 2008, 120, 1131 - 1134
33. Angew. Chem. Int. Ed. 2008, 47, 1115 - 1118
34. K. Inamoto, T. Saito, K. Hiroya, T. Doi, Synlett 2008, 3157 - 3162
35. K. Inamoto, T. Saito, M. Katsuno, T. Sakamoto, K. Hiroya, Org. Lett. 2007, 9, 2931 - 2934
36. H.-Y. Thu, W.-Y. Yu, C.-M. Che, J. Am. Chem. Soc. 2006, 128, 9048 - 9049
37. W. C. P. Tsang, N. Zheng, S. L. Buchwald, J. Am. Chem. Soc. 2005, 127, 14560 - 14561.
38. Examples of C-S bond formation via catalytic C-H functionalization in the presence of transition metals are much rarer in the literature, see
39. J. Zhu, Z. Chen, H. Xie, S. Li, Y. Wu, Org. Lett. 2010, 12, 2434 - 2436
40. X. Zhao, E. Dimitrijević, V. M. Dong, J. Am. Chem. Soc. 2009, 131, 3466 - 3467
41. L. L. Joyce, R. A. Batey, Org. Lett. 2009, 11, 2792 - 2795
42. K. Inamoto, Y. Arai, K. Hiroya, T. Doi, Chem. Commun. 2008, 5529 - 5531
43. K. Inamoto, C. Hasegawa, K. Hiroya, T. Doi, Org. Lett. 2008, 10, 5147 - 5150.
44. The 2-arylbenzothiazole nucleus is considered to be a privileged structure in medicinal chemistry. For a review, see:, A. A. Weekes, A. D. Westwell, Curr. Med. Chem. 2009, 16, 2430 - 2440
45. for a recent review on benzothiazole alkaloids, see:, L. L. Bozec, C. J. Moody, Aust. J. Chem. 2009, 62, 639 - 647.
46. For selected recent reports on the synthesis of 2-arylbenzothiazoles, see
47. G. Li, Y. Peng, Monatsh. Chem. 2010, 141, 45 - 48
48. D. Ma, S. Xie, P. Xue, X. Zhang, J. Dong, Y. Jiang, Angew. Chem. 2009, 121, 4286 - 4289
49. Angew. Chem. Int. Ed. 2009, 48, 4222 - 4225
50. R. Fazaeli, H. Aliyan, Appl. Catal. A 2009, 353, 74 - 79
51. K. Bahrami, M. M. Khodaei, F. Naali, Synlett 2009, 569 - 572
52. Q. Ding, X.-G. Huang, J. Wu, J. Comb. Chem. 2009, 11, 1047 - 1049
53. U. R. Pratap, J. R. Mali, D. V. Jawale, R. A. Mane, Tetrahedron Lett. 2009, 50, 1352 - 1354
54. D. Azarifar, B. Maleki, M. Setayeshnazar, Phosphorus, Sulfur, and Silicon 2009, 184, 2097 - 2102
55. T. Mase, T. Itoh, Pure Appl. Chem. 2008, 80, 707 - 715
56. F. Al-Qalaf, R. A. Mekheimer, K. U. Sadek, Molecules 2008, 13, 908 - 2914
57. S. S. Pawar, D. V. Dekhane, M. S. Shingare, S. N. Thore, Aust. J. Chem. 2008, 61, 905 - 909.
58. For the synthesis of 2-substituted benzothiazoles from N-(2-halophenyl)thiobenzamides via palladium- or copper-catalyzed C-X (X=halogen atom) functionalization followed by intramolecular S-arylation, see
59. P. Saha, T. Ramana, N. Purkait, M. A. Ali, R. Paul, T. Punniyamurthy, J. Org. Chem. 2009, 74, 8719 - 8725
60. M. D. Vera, J. C. Pelletier, J. Comb. Chem. 2007, 9, 569 - 570
61. L. L. Joyce, G. Evindar, R. A. Batey, Chem. Commun. 2004, 446 - 447
62. C. Benedí, F. Bravo, P. Uriz, E. Fernández, C. Claver, S. Castillón, Tetrahedron Lett. 2003, 44, 6073 - 6077.
63. For selected reviews on palladium-catalyzed oxidation reactions using molecular oxygen, see
64. K. M. Gligorich, M. S. Sigman, Chem. Commun. 2009, 3854 - 3867
65. J. Muzart, Chem. Asian J. 2006, 1, 508 - 515
66. S. S. Stahl, Science 2005, 309, 1824 - 1826
67. T. Punniyamurthy, S. Velusamy, J. Iqbal, Chem. Rev. 2005, 105, 2329 - 2363
68. S. S. Stahl, Angew. Chem. 2004, 116, 3480 - 3501
69. Angew. Chem. Int. Ed. 2004, 43, 3400 - 3420
70. T. Nishimura, S. Uemura, Synlett 2004, 201 - 216.
71. [2f,2i, 2j,2n, 3c]
72. 2 as a terminal co-reoxidant, see
73. S. Ueda, H. Nagasawa, J. Org. Chem. 2009, 74, 4272 - 4277
74. G. Brasche, S. L. Buchwald, Angew. Chem. 2008, 120, 1958 - 1960
75. Angew. Chem. Int. Ed. 2008, 47, 1932 - 1934
76. G. Brasche, J. García-Fortanet, S. L. Buchwald, Org. Lett. 2008, 10, 2207 - 2210
77. E. M. Ferreira, H. Zhang, B. M. Stoltz, Tetrahedron 2008, 64, 5987 - 6001
78. T. A. Dwight, N. R. Rue, D. Charyk, R. Josselyn, B. DeBoef, Org. Lett. 2007, 9, 3137 - 3139
79. X. Chen, X.-S. Hao, C. E. Goodhue, J.-Q. Yu, J. Am. Chem. Soc. 2006, 128, 6790 - 6791.
80. For a review, see:, A. Corsaro, V. Pistarà, Tetrahedron 1998, 54, 15027 - 15062.
81. For selected examples, see
82. N. Ramnath, V. Ramesh, V. Ramamurthy, J. Org. Chem. 1983, 48, 214 - 222
83. S. Tamagaki, R. Akatsuka, M. Nakamura, S. Kozuka, Tetrahedron Lett. 1979, 3665 - 3668
84. J. E. Gano, S. Atik, Tetrahedron Lett. 1979, 4635 - 4636
85. L. Carlsen, J. Org. Chem. 1976, 41, 2971 - 2973
86. N. Ishibe, M. Odani, M. Sunami, J. Chem. Soc. B 1971, 1837 - 1840
87. L. Gattermann, H. Schultze, Ber. Dtsch. Chem. Ges. 1896, 29, 2944 - 2945.
88. F. Shibahara, A. Suenami, A. Yoshida, T. Murai, Chem. Commun. 2007, 2354 - 2356.
89. 2 and 50 mol% of CsF in DMSO (0.05M) at 120°C for 2 h under an argon atmosphere provided the desired product 2a in only 14% yield along with the formation of by-product 3a in 76% yield.
90. 4 gave relatively lower yields.
91. For selected recent reports on synthesis of 2-aminobenzothiazoles, see
92. Y.-J. Guo, R.-Y. Tang, P. Zhong, J.-H. Li, Tetrahedron Lett. 2010, 51, 649 - 652
93. F. Piscitelli, C. Ballatore, A. B. Smith III, Bioorg. Med. Chem. Lett. 2010, 20, 644 - 648
94. S.-S. Pi, X.-G. Zhang, R.-Y. Tang, J.-H. Li, Synlett 2009, 3032 - 3036
95. Q. Ding, X. He, J. Wu, J. Comb. Chem. 2009, 11, 587 - 591
96. Z. Li, S. Xiao, G. Tian, A. Zhu, X. Feng, J. Liu, Phosphorus, Sulfur, and Silicon 2008, 183, 1124 - 1133.
97. Side reactions, such as conversion of thioureas into the corresponding urea compounds, were not observed.
98. Addition of CsF had no effect on cyclization in this case.
99. Similar domino-type synthesis of 2-aminobenzothiazoles via C-X (X=halogen atom) functionalization using aryl isothiocyanates as starting materials has previously been reported, see
100. iron catalysis:, J.-W. Qui, X.-G. Zhang, R.-Y. Tang, P. Zhong, J.-H. Li, Adv. Synth. Catal. 2009, 351, 2319 - 2323
101. [6c,15a,15d]
102. For selected examples in which an electrophilic aromatic palladation pathway is proposed, see
103. E. M. Beck, N. P. Grimster, R. Haltey, M. J. Gaunt, J. Am. Chem. Soc. 2006, 128, 2528 - 2529
104. B. S. Lane, M. A. Brown, D. Sames, J. Am. Chem. Soc. 2005, 127, 8050 - 8057
105. A. L. Bowie, Jr., C. C. Hughes, D. Trauner, Org. Lett. 2005, 7, 5207 - 5209
106. C.-H. Park, V. Ryabova, I. V. Seregin, A. W. Sromek, V. Gevorgyan, Org. Lett. 2004, 6, 1159 - 1162
107. B. Glover, K. A. Harvey, B. Liu, M. J. Sharp, M. F. Tymoschenko, Org. Lett. 2003, 5, 301 - 304
108. E. J. Hennessy, S. L. Buchwald, J. Am. Chem. Soc. 2003, 125, 12084 - 12085
109. W. Li, D. P. Nelson, M. S. Jensen, R. S. Hoerner, G. J. Javadi, D. Cai, R. D. Larsen, Org. Lett. 2003, 5, 4835 - 4837
110. A. M. Echavarren, B. Gómez-Lor, J. J. González, de Frutos, Synlett 2003, 585 - 597
111. S. Pivsa-Art, T. Satoh, Y. Kawamura, M. Miura, M. Nomura, Bull. Chem. Soc. Jpn. 1998, 71, 467 - 473.
112. J.-X. Wang, J. A. McCubbin, M. Jin, R. S. Laufer, Y. Mao, A. P. Crew, M. J. Mulvihill, V. Snieckus, Org. Lett. 2008, 10, 2923 - 2926
113. [2i]
114. M. Toyota, A. Ilangovan, R. Okamoto, T. Masaki, M. Arakawa, M. Ihara, Org. Lett. 2002, 4, 4293 - 4296.
115. For selected examples, see
116. B. Liégault, D. Lapointe, L. Caron, A. Vlassova, K. Fagnou, J. Org. Chem. 2009, 74, 1826 - 1834
117. S. Pascual, P. de Mendoza, A. A. C. Braga, F. Maseras, A. M. Echavarren, Tetrahedron 2008, 64, 6021 - 6029
118. N. Chernyak, V. J. Gevorgyan, J. Am. Chem. Soc. 2008, 130, 5636 - 5637
119. S. J. Hwang, S. H. Cho, S. Chang, J. Am. Chem. Soc. 2008, 130, 16158 - 16159
120. S. Würtz, S. Rakshit, J. J. Neumann, T. Dröge, F. Glorius, Angew. Chem. 2008, 120, 7340 - 7343
121. Angew. Chem. Int. Ed. 2008, 47, 7230 - 7233
122. L.-C. Campeau, M. Parisien, A. Jean, K. Fagnou, J. Am. Chem. Soc. 2006, 128, 581 - 590
123. D. García-Cuadrado, A. A. C. Braga, F. Maseras, A. M. Echavarren, J. Am. Chem. Soc. 2006, 128, 1066 - 1067
124. D. L. Davies, S. M. A. Donald, S. A. Macgregor, J. Am. Chem. Soc. 2005, 127, 13754 - 13755
125. A. J. Mota, A. Dedieu, C. Bour, J. Suffert, J. Am. Chem. Soc. 2005, 127, 7171 - 7182
126. [19f]
127. D) values observed in related aromatic palladation processes, see
128. [21c] (intramolecular: 3.5, intremolecular: 2.6)
129. [21d] (intramolecular: 1.4, intremolecular: 1.7)
130. [21e] (intramolecular: 4.6)
131. Z. Shi, B. Li, X. Wan, J. Cheng, Z. Fang, B. Cao, C. Qin, Y. Wang, Angew. Chem. 2007, 119, 5650 - 5654
132. Angew. Chem. Int. Ed. 2007, 46, 5554 - 5558 (intramolecular: 2.3)
133. [21g] (intramolecular: 5.0-6.7)
134. M. D. K. Boele, G. P. F. van Strijdonck, A. H. M. de Vries, P. C. J. Kamer, J. G. de Vries, P. W. N. M. van Leeuwen, J. Am. Chem. Soc. 2002, 124, 1586 - 1587 (intramolecular: 3.0). For experimental details, see Supporting Information.
135. A study of kinetic isotope effects for 2-aminobenzothiazole synthesis was also performed, which resulted in the observation of low KIE value (intramolecular: 1.2). Further investigation is necessary to reveal the precise reaction mechanism for this process. For experimental details, see Supporting Information.
136. [21f]
137. Sanford also reported the comparable reactivity between electron-rich arenes and electron-poor arenes (1.3:1) in the Pd-catalyzed oxidative coupling reactions involving σ-bond metathesis, see:, K. L. Hull, M. S. Sanford, J. Am. Chem. Soc. 2009, 131, 9651 - 9653.
138. [21i]
139. In spite of the experimental results shown in Figure 1 and Figure 2, both electrophilic aromatic palladation and Heck-like insertion pathways cannot be completely ruled out at present and further mechanistic studies are necessary. For example, in some cases, electrophilic aromatic substitution reactions exhibit certain KIE values, see:, X. Zhao, C. S. Yeung, V. M. Dong, J. Am. Chem. Soc. 2010, 132, 5837 - 5844 (KIE=3.1-3.9) and references cited therein.
140. CsF was previously shown to have a superior effect to LiF, NaF, and KF, presumably due to its higher solubility, in Pd-catalyzed reductive homocoupling of aryl halides, see
141. W. M. Seganish, M. E. Mowery, S. Riggleman, P. DeShong, Tetrahedron 2005, 61, 2117 - 2121
142. C. Qi, X. Sun, C. Lu, J. Yang, Y. Du, H. Wu, X.-M. Zhang, J. Organomet. Chem. 2009, 694, 2912 - 2916.
143. Use of an increased or decreased amount of CsF, instead of 50 mol%, gave relatively lower yields. For details, see Supporting Information.
144. K. Okamoto, T. Yamamoto, T. Kanbara, Synlett 2007, 2687 - 2690.
145. G. Evindar, R. A. Batey, J. Org. Chem. 2006, 71, 1802 - 1808.
146. A. Martvoň, J. Surá, M. Černayová, Collect. Czech. Chem. Commun. 1974, 39, 1356 - 1364.
147. M. F. G. Stevens, C. J. McCall, P. Lelieveld, P. Alexander, A. Richter, D. E. Daviess, J. Med. Chem. 1994, 37, 1689 - 1695.
148. N. K. Downer, Y. A. Jackson, Org. Biomol. Chem. 2004, 2, 3039 - 3043.
149. R. J. Perry, B. D. Wilson, Organometallics 1994, 13, 3346 - 3350.
150. S. N. Sawhney, P. Sharma, K. Bajaj, A. Gupta, Synth. Commun. 1993, 23, 263 - 270.
151. G. L. Oliver, J. R. Dann, J. W. Gates Jr, J. Am. Chem. Soc. 1958, 80, 702 - 707.
152. S. Ohno, K. Mizukoshi, K. Izumi, K. Kato, M. Hori, Chem. Pharm. Bull. 1988, 36, 551 - 562.
153. A. Couture, P. Grandclaudon, E. Huguerre, J. Heterocycl. Chem. 1987, 24, 1765 - 1769.
154. P. A. S. Smith, D. W. Emerson, J. Am. Chem. Soc. 1960, 82, 3076 - 3082.
155. M. Sekiya, A. Hara, T. Masui, Chem. Pharm. Bull. 1963, 11, 277 - 283.
156. S. P. Kharida, P. R. Pathan, P. S. Satpanthi, J. J. Trivedi, J. Indian Chem. Soc. 1960, 37, 705 - 709.
157. I. A. Kaye, C. L. Parris, J. Org. Chem. 1951, 16, 1859 - 1863.
158. R. A. Henry, W. M. Dehn, J. Am. Chem. Soc. 1950, 72, 2806.
159. G. Shen, X. Lv, W. Bao, Eur. J. Org. Chem. 2009, 5897 - 5901.
160. M. Sakamoto, K. Miyazawa, Y. Tomimatsu, Chem. Pharm. Bull. 1976, 24, 2532 - 2540.
161. R. Fioravanti, M. Biava, G. C. Porretta, Heterocycles 1994, 37, 367 - 377.
162. M. Kienle, C. Dunst, P. Knochel, Org. Lett. 2009, 11, 5158 - 5161.