865186-94-3Relevant articles and documents
Enzyme-like Supramolecular Iridium Catalysis Enabling C?H Bond Borylation of Pyridines with meta-Selectivity
Al-Shehimy, Shaymaa,Gramage-Doria, Rafael,Roisnel, Thierry,Trouvé, Jonathan,Zardi, Paolo
supporting information, p. 18006 - 18013 (2021/05/07)
The use of secondary interactions between substrates and catalysts is a promising strategy to discover selective transition metal catalysts for atom-economy C?H bond functionalization. The most powerful catalysts are found via trial-and-error screening due to the low association constants between the substrate and the catalyst in which small stereo-electronic modifications within them can lead to very different reactivities. To circumvent these limitations and to increase the level of reactivity prediction in these important reactions, we report herein a supramolecular catalyst harnessing Zn???N interactions that binds to pyridine-like substrates as tight as it can be found in some enzymes. The distance and spatial geometry between the active site and the substrate binding site is ideal to target unprecedented meta-selective iridium-catalyzed C?H bond borylations with enzymatic Michaelis–Menten kinetics, besides unique substrate selectivity and dormant reactivity patterns.
meta-Nitration of Arenes Bearing ortho/para Directing Group(s) Using C?H Borylation
Li, Xuejing,Deng, Xingwang,Coyne, Anthony G.,Srinivasan, Rajavel
supporting information, p. 8018 - 8023 (2019/05/29)
Herein, we report the meta-nitration of arenes bearing ortho/para directing group(s) using the iridium-catalyzed C?H borylation reaction followed by a newly developed copper(II)-catalyzed transformation of the crude aryl pinacol boronate esters into the corresponding nitroarenes in a one-pot fashion. This protocol allows the synthesis of meta-nitrated arenes that are tedious to prepare or require multistep synthesis using the existing methods. The reaction tolerates a wide array of ortho/para-directing groups, such as ?F, ?Cl, ?Br, ?CH3, ?Et, ?iPr ?OCH3, and ?OCF3. It also provides regioselective access to the nitro derivatives of π-electron-deficient heterocycles, such as pyridine and quinoline derivatives. The application of this method is demonstrated in the late-stage modification of complex molecules and also in the gram-scale preparation of an intermediate en route to the FDA-approved drug Nilotinib. Finally, we have shown that the nitro product obtained by this strategy can also be directly converted to the aniline or hindered amine through Baran's amination protocol.
WNT PATHWAY MODULATORS
-
Paragraph 0340; 0341, (2015/07/07)
The present invention relates to dihydropyrazolo[l,5-a]pyrimidine compounds of formula I, defined herein, as WNT pathways modulators, processes for making them, and pharmaceutical compositions comprising them. Methods of treatment of conditions mediated by WNT pathway signalling including cancer, fibrosis, stem cell and diabetic retinopathy, rheumatoid arthritis, psoriasis and myocardial infarction, comprising the compounds of formula I are also provided.