We report the facile amide-forming ligation of acylsilanes with hydroxylamines (ASHA ligation) under aqueous conditions. The ligation is fast, chemoselective, mild, high-yielding and displays excellent functional-group tolerance. Late-stage modifications of an array of marketed drugs, peptides, natural products, and biologically active compounds showcase the robustness and functional-group tolerance of the reaction. The key to the success of the reaction could be the possible formation of the strong SiÀO bond via a Brook-type rearrangement. Given its simplicity and efficiency, this ligation has the potential to unfold new applications in the areas of medicinal chemistry and chemical biology.
Potassium
acyltrifluoroborates (KATs) are opening up new avenues
in chemical biology, materials science, and synthetic organic chemistry
due to their intriguing reactivities. However, the synthesis of these
compounds remains mostly complicated and time-consuming. Herein, we
have developed chemoselective Pd-catalyzed approaches for the late-stage
diversification of arenes bearing prefunctionalized KATs. These approaches
feature chemoselective cross-coupling, rapid diversification, functional
group tolerance, mild reaction conditions, simple operation, and high
yields.
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.
Herein, we disclose the first set of unique selenium-containing SLAP (SiLicon Amine Protocol) reagents for the direct synthesis of C3/C5-substituted selenomorpholines and 1,4-selenazepanes from diverse (hetero)aldehydes under mild photocatalytic conditions....
We report the first set of selenium-containing SnAP reagents for the direct synthesis of C-substituted selenomorpholines and 1,4-selenazepanes and the biological evaluation of these elusive N-heterocycles.
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