159454-73-6Relevant articles and documents
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.
Synthetic and mechanistic studies on the azabicyclo[7.3.1]enediyne core and naphtho[2,3-h]quinoline portions of dynemicin A
Magnus, Philip,Eisenbeis, Shane A.,Fairhurst, Robin A.,Iliadis, Theodore,Magnus, Nicholas A.,Parry, David
, p. 5591 - 5605 (2007/10/03)
The synthesis of the 13-keto-10-azabicyclo[7.3.1]enediyne core structure of dynemicin A has been achieved by two routes, Schemes 4 and 6. The chemistry of the 13-keto core structure is dominated by the unusually facile bridgehead enolization. Comparison of the rates of cycloaromatization of a variety of enediynes revealed that substantial rate differences occurred even though the distance between the bonding acetylenes was virtually identical. A non-radical cycloaromatization pathway, initiated by thiol addition to the enediyne system, was discovered, and the simple core amine 26 exhibits modest in vitro and in vivo antitumor activity. Finally, two methods for the synthesis of the naphtho[2,3-h]quinoline portion of dynemicin A are described, and both these compounds also exhibit antitumor activity.
Short Synthesis of the Dynemicin Core Structure: Unusual Bridgehead Enolate Raectivity
Magnus, Philip,Parry, David,Iliadis, Theodore,Eisenbeis, Shane A.,Fairhurst, Robin A.
, p. 1543 - 1544 (2007/10/02)
The dynemicin core azabicycloenediyne 2 is readily synthesized in five steps from the quinolines 9 or 13; the chemistry of the core enediyne is dominated by its ready enolization.
