Modular preparation of cationic bipyridines and azaarenes <i>via</i> C–H activation

King, Ryan P.; Yang, Jenny Y.

doi:10.1039/d3sc04864k

Cited by 1 publication

(2 citation statements)

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“…N-oxide 28 was accessible in 70% isolated yield using a Pd-catalyzed Fagnou-type cross-coupling of 1-bromo-3,4-(methylenedioxy)benzene and quinoline Noxide (Scheme 3). Using our modification to Xiong and Hoye's C−H trimethylamination conditions, 40,52 we accessed spectroscopically pure 4-trimethylaminated quinoline 29 in 42% isolated yield following salt metathesis with sodium tetrafluoroborate. Isolated 29 can subsequently react with sodium methoxide to form Graveolinine (27) in 62% isolated yield.…”

Section: Table 3 Scope Of Accessible C−f Bonds Amentioning

confidence: 99%

“…Unfortunately, few substituted halobipyridines are commercially available and their preparation can be challenging. , Additionally, separation of S N Ar products from unreacted starting material by silica gel column chromatography can be difficult . Since we previously reported a general, modular, and scalable approach to accessing trimethylammonium-substituted 2,2′-bipyridines and azaarenes, we wondered if they could also function as precursors to a variety of substituted bipyridines. If successful, their application would have numerous benefits over using 6-halobipyridines as electrophiles, including ease of access to more highly functionalized ligands, and more facile purification from unreacted trimethylammonium bipyridine.…”

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confidence: 99%

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Diversification of Bipyridines and Azaheterocycles via Nucleophilic Displacement of Trimethylammoniums

Yang,

King

2024

ACS Org. Inorg. Au

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Bipyridines and azaarenes are an important class of ligands that impart unique and tunable properties to transition metal complexes and catalysts. While some derivatives are commercially available, noncommercial analogues are often challenging to prepare and purify. Herein, we report a general nucleophilic aromatic substitution reaction that converts cationic trimethylaminated bipyridines into a series of functionalized bipyridines. Our method showcases a series of C−O, C−S, and C−F bond-forming reactions as well as a selective monodemethylation that converts the electron-deficient trimethylammonium to an electron-rich dimethylamine. The approach was further applied to diversification of pharmaceuticals and natural products and was applied to the total synthesis of Graveolinine and the preparation of Graveolinine derivatives.

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Section: Table 3 Scope Of Accessible C−f Bonds Amentioning

confidence: 99%

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confidence: 99%