Cart
Communication
Easily Attachable and Detachable ortho-Directing Agent for Arylboronic Acids in Ruthenium-Catalyzed Aromatic C−H Silylation
Full Text HTML
Hi-Res PDFPurchase the full-text
- PDF/HTML,
figures/images,
references and tables,
(where available)
Temporary graduate student from Sumitomo Chemical Co., Ltd.
Abstract
o-C−H silylation of arylboronic acids has been achieved using 2-pyrazol-5-ylaniline as an ortho-directing agent, which was temporarily attached to the boronyl group via Ru-catalyzed silylation with hydrosilanes. Condensation products of arylboronic acids with 2-pyrazol-5-ylaniline were prepared in situ and subjected to reaction with triorganosilanes in the presence of RuH2(CO)(PPh3)3 at 135 °C. Regioselective silylation at their ortho-positions proceeded in good yields for phenylboronic acids bearing para-substituents such as chloro, fluoro, methyl, methoxy, and trifluoromethyl groups. p-Methoxycarbonyl-substituted phenylboronic acid provided the corresponding silylated product in moderate yield. m-Tolyl- and 2-naphthylboronic acids underwent silylation selectively at the less sterically hindered ortho-positions. The silylated products were utilized in Suzuki−Miyaura coupling, followed either by iodination with ICl or by Tamao oxidation to furnish iodine- or hydroxy-substituted biaryls.
Citing Articles
Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.
This article has been cited by 10 ACS Journal articles (5 most recent appear below).
Silanol: A Traceless Directing Group for Pd-Catalyzed o-Alkenylation of Phenols
Chunhui Huang, Buddhadeb Chattopadhyay, and Vladimir GevorgyanJournal of the American Chemical Society2011 Article ASAPSilanol: A Traceless Directing Group for Pd-Catalyzed o-Alkenylation of Phenols
Chunhui Huang, Buddhadeb Chattopadhyay, and Vladimir GevorgyanJournal of the American Chemical Society2011 Article ASAPA silanol-directed, Pd(II)-catalyzed C–H alkenylation of phenols is reported. This work features silanol, as a novel traceless directing group, and a directed o-C–H alkenylation of phenols. This new method allows for efficient synthesis of diverse ...
Anthranilamide: A Simple, Removable ortho-Directing Modifier for Arylboronic Acids Serving also as a Protecting Group in Cross-Coupling Reactions
Hideki Ihara, Masashi Koyanagi, and Michinori SuginomeOrganic Letters2011 Article ASAPAnthranilamide: A Simple, Removable ortho-Directing Modifier for Arylboronic Acids Serving also as a Protecting Group in Cross-Coupling Reactions
Hideki Ihara, Masashi Koyanagi, and Michinori SuginomeOrganic Letters2011 Article ASAPAnthranilamide (AAM) serves as a bifunctional modifier on the boron atom in catalytic transformations of arylboronic acids. It makes boronyl groups unreactive in Suzuki–Miyaura coupling and promotes Ru-catalyzed ortho-silylation. Suzuki–Miyaura coupling ...
Divergent C–H Functionalizations Directed by Sulfonamide Pharmacophores: Late-Stage Diversification as a Tool for Drug Discovery
Hui-Xiong Dai, Antonia F. Stepan, Mark S. Plummer, Yang-Hui Zhang, and Jin-Quan YuJournal of the American Chemical Society2011 Article ASAPDivergent C–H Functionalizations Directed by Sulfonamide Pharmacophores: Late-Stage Diversification as a Tool for Drug Discovery
Hui-Xiong Dai, Antonia F. Stepan, Mark S. Plummer, Yang-Hui Zhang, and Jin-Quan YuJournal of the American Chemical Society2011 Article ASAPModern drug discovery is contingent on identifying lead compounds and rapidly synthesizing analogues. The use of a common pharmacophore to direct multiple and divergent C–H functionalizations of lead compounds is a particularly attractive approach. Herein,...
Palladium-Catalyzed Oxidative Allylic C−H Silylation
Johanna M. Larsson, Tony S. N. Zhao, and Kálmán J. SzabóOrganic Letters2011 13 (7), 1888-1891Palladium-Catalyzed Oxidative Allylic C−H Silylation
Johanna M. Larsson, Tony S. N. Zhao, and Kálmán J. SzabóOrganic Letters2011 13 (7), 1888-1891Palladium-catalyzed allylic C−H silylation was performed with use of hexamethyldisilane as the silyl source. These C−H functionalization reactions occur only in the presence of hypervalent iodine reagents or other strong oxidants and proceed with ...
Cooperative Catalytic Activation of Si−H Bonds by a Polar Ru−S Bond: Regioselective Low-Temperature C−H Silylation of Indoles under Neutral Conditions by a Friedel−Crafts Mechanism
Hendrik F. T. Klare, Martin Oestreich, Jun-ichi Ito, Hisao Nishiyama, Yasuhiro Ohki, and Kazuyuki TatsumiJournal of the American Chemical Society2011 133 (10), 3312-3315Cooperative Catalytic Activation of Si−H Bonds by a Polar Ru−S Bond: Regioselective Low-Temperature C−H Silylation of Indoles under Neutral Conditions by a Friedel−Crafts Mechanism
Hendrik F. T. Klare, Martin Oestreich, Jun-ichi Ito, Hisao Nishiyama, Yasuhiro Ohki, and Kazuyuki TatsumiJournal of the American Chemical Society2011 133 (10), 3312-3315Merging cooperative Si−H bond activation and electrophilic aromatic substitution paves the way for C-3-selective indole C−H functionalization under electronic and not conventional steric control. The Si−H bond is heterolytically split by the Ru−S bond of ...
Tools
-
Add to Favorites
-
Download Citation
-
Email a Colleague -
Permalink
Order Reprints
Rights & Permissions
Citation Alerts
History
- Published In Issue June 10, 2009
- Article ASAPMay 12, 2009
- Received: March 24, 2009
ACS
Network
Facebook
Tweet This
CiteULike
Newsvine
Digg This
Delicious
