Iridium-Catalyzed Silylation of Aryl C–H Bonds
作者： Chen Cheng , John F. Hartwig
DOI: 10.1021/JA511352U
关键词: Organic chemistry 、 Surface modification 、 Medicinal chemistry 、 Catalysis 、 Silylation 、 Regioselectivity 、 Iridium 、 Aryl 、 Halogenation 、 Chemistry 、 Steric effects
摘要: A method for the iridium-catalyzed silylation of aryl C–H bonds is described. The reaction HSiMe(OSiMe3)2 with arenes and heteroarenes catalyzed by combination [Ir(cod)(OMe)]2 2,4,7-trimethylphenanthroline occurs aromatic compound as limiting reagent high levels sterically derived regioselectivity. This new catalytic system a much higher tolerance functional groups than previously reported rhodium-catalyzed wide range heteroarenes. silylarene products are suitable further transformations, such oxidation, halogenation, cross-coupling. Late-stage functionalization complex pharmaceutical compounds was demonstrated.
acs.org
sci-hub.se 参考文章(36)
Ibraheem A. I. Mkhalid, Jonathan H. Barnard, Todd B. Marder, Jaclyn M. Murphy, John F. Hartwig, C−H Activation for the Construction of C−B Bonds Chemical Reviews. ,vol. 110, pp. 890- 931 ,(2010) , 10.1021/CR900206P
Matthew A. Larsen, John F. Hartwig, Iridium-Catalyzed C–H Borylation of Heteroarenes: Scope, Regioselectivity, Application to Late-Stage Functionalization, and Mechanism Journal of the American Chemical Society. ,vol. 136, pp. 4287- 4299 ,(2014) , 10.1021/JA412563E
Gyeongshin Choi, Hayato Tsurugi, Kazushi Mashima, Hemilabile N-Xylyl-N′-methylperimidine Carbene Iridium Complexes as Catalysts for C–H Activation and Dehydrogenative Silylation: Dual Role of N-Xylyl Moiety for ortho-C–H Bond Activation and Reductive Bond Cleavage Journal of the American Chemical Society. ,vol. 135, pp. 13149- 13161 ,(2013) , 10.1021/JA406519U
Miki Murata, Naoaki Fukuyama, Jun-ichi Wada, Shinji Watanabe, Yuzuru Masuda, Platinum-catalyzed Aromatic C–H Silylation of Arenes with 1,1,1,3,5,5,5-Heptamethyltrisiloxane Chemistry Letters. ,vol. 36, pp. 910- 911 ,(2007) , 10.1246/CL.2007.910
Fumitoshi Kakiuchi, Kimitaka Igi, Mitsutaka Matsumoto, Naoto Chatani, Shinji Murai, Ruthenium-Catalyzed Dehydrogenative Silylation of Aryloxazolines with Hydrosilanes via C–H Bond Cleavage Chemistry Letters. ,vol. 2001, pp. 422- 423 ,(2001) , 10.1246/CL.2001.422
Soichiro Kawamorita, Hirohisa Ohmiya, Kenji Hara, Atsushi Fukuoka, Masaya Sawamura, Directed Ortho Borylation of Functionalized Arenes Catalyzed by a Silica-Supported Compact Phosphine−Iridium System Journal of the American Chemical Society. ,vol. 131, pp. 5058- 5059 ,(2009) , 10.1021/JA9008419
Kohei Tamao, Neyoshi Ishida, Tatsu Tanaka, Makoto Kumada, Silafunctional compounds in organic synthesis. Part 20. Hydrogen peroxide oxidation of the silicon-carbon bond in organoalkoxysilanes Organometallics. ,vol. 15, pp. 1694- 1696 ,(1983) , 10.1021/OM50005A041
Yasuo Hatanaka, Tamejiro Hiyama, Cross-coupling of organosilanes with organic halides mediated by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate Journal of Organic Chemistry. ,vol. 53, pp. 918- 920 ,(1988) , 10.1021/JO00239A056
Carl W. Liskey, John F. Hartwig, Iridium-Catalyzed C–H Borylation of Cyclopropanes Journal of the American Chemical Society. ,vol. 135, pp. 3375- 3378 ,(2013) , 10.1021/JA400103P
Tatsuo Ishiyama, Jun Takagi, Kousaku Ishida, Norio Miyaura, Natia R. Anastasi, John F. Hartwig, Mild iridium-catalyzed borylation of arenes. High turnover numbers, room temperature reactions, and isolation of a potential intermediate. Journal of the American Chemical Society. ,vol. 124, pp. 390- 391 ,(2002) , 10.1021/JA0173019