85370-85-0Relevant articles and documents
Directed Metalation-Suzuki-Miyaura Cross-Coupling Strategies: Regioselective Synthesis of Hydroxylated 1-Methyl-phenanthrenes
J?rgensen, K?re B.,Rantanen, Toni,D?rfler, Thilo,Snieckus, Victor
, p. 9410 - 9424 (2015/10/12)
A general, efficient, and regioselective synthesis of a series of hydroxylated 1-methylphenanthrenes 9 by a combined directed ortho metalation (DoM)-Suzuki-Miyaura cross-coupling-directed remote metalation (DreM) sequence is reported. Diversity to this methodology was achieved by a regioselective DoM rather than DreM reaction, affording more highly substituted phenanthrols (Table 2). Application of the turbo-Grignard reagent (i-PrMgCl·LiCl) in the Ni-catalyzed Corriu-Kumada reaction gave efficient decarbamoylation (Tables 3and 4). Additional features are the TMS protecting group and halo-induced ipso-desilylation tactics applied to the regioselective synthesis of phenanthrenes (Scheme 2).
Iridium-catalyzed C-H activation versus directed ortho metalation: Complementary borylation of aromatics and heteroaromatics
Hurst, Timothy E.,Macklin, Todd K.,Becker, Maike,Hartmann, Eduard,Kuegel, Wolfgang,Parisienne-LaSalle, Jean-Christophe,Batsanov, Andrei S.,Marder, Todd B.,Snieckus, Victor
supporting information; experimental part, p. 8155 - 8161 (2010/09/18)
Systematic studies are presented demonstrating the complementarity of directed ortho metalation (DoM) and Ir-catalyzed strategies for the provision of borylated aromatics and their subsequent Suzuki-Miyaura coupling reactions. A new concept, the use of the TMS group, readily introduced by DoM, as a latent regiodirective moiety to overcome the otherwise problematic production of isomeric borylated product mixtures is presented. Additional electrophile-induced ipso-deborylation and DoM reactions of the Bpin products are described.
Rational design of inhibitors of VirA-VirG two-component signal transduction
Maresh, Justin,Zhang, Jin,Tzeng, Yih-Ling,Goodman, Nora A.,Lynn, David G.
, p. 3281 - 3286 (2008/02/08)
VirA-VirG two-component system regulates the vir (virulence) operon in response to specific host factors (xenognosins) in the plant pathogen Agrobacterium tumefaciens. Using whole cell assays, stable inhibitors inspired by the labile natural benzoxazinone inhibitor HDMBOA are developed. It is found that aromatic aldehydes represent a minimal structural unit for activity. In particular, 3-hydroxy-4,6-dimethoxy-3H-isobenzofuran-1-one (HDI) was found to have the highest activity, making it the most potent developed inhibitor of virulence gene expression in Agrobacterium.
Directed Metalation Route to Ferroelectric Liquid Crystals with a Chiral Fluorenol Core: The Effect of Restricted Rotation on Polar Order
McCubbin, J. Adam,Tong, Xia,Wang, Ruiyao,Zhao, Yue,Snieckus, Victor,Lemieux, Robert P.
, p. 1161 - 1167 (2007/10/03)
A new series of smectic C* (SmC*) mesogens containing a chiral (R)-2-octyloxy side chain and either a fluorenone (2a-e) or chiral fluorenol (3a-e) core were synthesized using a combined directed ortho metalation-directed remote metalation strategy. The Sm
Directed Ortho Metalation of N,N-Diethylbenzamides. Silicon Protection of Ortho Sites and the o-Methyl Group
Mills, Robert J.,Taylor, Nicholas J.,Snieckus, Victor
, p. 4372 - 4385 (2007/10/02)
New general methodology of value in aromatic chemistry based on silicon protection of preferred ortho metalation sites in benzamides and o-methyl groups in o-toluamides (1, 2, Scheme I) is described.According to these methodologies, routes (Scheme II and V) to 1,2,5-, 1,2,4,5-, and 1,2,3-substituted aromatics with a variety of functionalities and oxidation states have been developed (Tables I and II).These tactics are used for the synthesis of difficult to access halo (10a-b, Scheme III) and methyl (21,25, Scheme VI) heterocycles.Ipso bromodesilylation reactions with bromine lead regiospecifically to o-bromobenzamides (12a,c, 14, Scheme IV).Walk-around-the-ring metalation processes provide highly substituted aromatics 27, 28, 29, and 30 (Scheme VII); the X-ray structure of the hexasubstituted derivative 30 shows a significant puckering of the aromatic ring.Cesium fluoride induced carbodesilylation of o-silylbenzamides with benzaldehyde affords, after TsOH cyclization, phthalides (31a-c, Scheme VIII) and constitutes a neutral alternative to the directed ortho metalation approach. α- and α,α-silylated o-toluamides are used in fluoride-mediated carbodesilylation (34a,d, Scheme IX) and desilylative Peterson olefination (35, Scheme X) procedures, respectively.The utility of α-silylated o-toluamide for the synthesis of a tetralin (38, Scheme XI) via an o-quinodimethane species is given.
