3,4,5-Triarylisothiazoles via C-C coupling chemistry

被引:23
作者
Christoforou, Irene C. [1 ]
Koutentis, Panayiotis A. [1 ]
机构
[1] Univ Cyprus, Dept Chem, CY-1678 Nicosia, Cyprus
关键词
D O I
10.1039/b702154b
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The regiocontrolled preparation of triarylisothiazoles is presented. 3-Halo-5-phenylisothiazole-4- carbonitriles, 1 (hal = Cl) and 18 ( hal = I), are converted into the corresponding 4- bromo derivatives 5 (3-hal = Cl) and 24 (3-hal = I) via a Hunsdiecker strategy while the 4- iodo analogues 7 (3-hal = Cl) and 22 (3-hal = I) are prepared via a Hoffmann and Sandmeyer strategy. Regioselective Suzuki, Stille and Negishi reactions occur at C-4 with both the 4- bromo-and 4- iodoisothiazoles 5 and 7, the latter being more reactive than the former. 3-Iodoisothiazoles 22 and 24 fail to give regiocontrolled Suzuki, Stille or Negishi couplings, however, 4- bromo-3-iodo-5-phenylisothiazole 24 gives the regiospecific palladium catalysed Ullmann-type reaction product 3,3'-bi(4-bromo-5-phenylisothiazole) 25. Alkali hydrolysis of 3-chloro-4,5-diphenylisothiazole 8 gives the 3-hydroxy analogue 12 which is converted into 3-bromo-4,5-diphenylisothiazole 13 with POBr3. 3-Bromoisothiazole 13 reacts with phenylzinc chloride to give 3,4,5-triphenylisothiazole 17 but fails to undergo effective Suzuki or Stille couplings. 3,5-Diphenylisothiazole-4-carbonitrile 26 is converted into the 4- bromo- and 4- iodo-3,5-diphenylisothiazoles 30 and 34 both of which are effective for Suzuki and Stille couplings. A series of triarylisothiazoles are prepared in this manner and fully characterised.
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页码:1381 / 1390
页数:10
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