Deaminative coupling of benzylamines and arylboronic acids

Sirvinskaite, Giedre; Reisenbauer, Julia C.; Morandi, Bill

doi:10.1039/d2sc06055h

Cited by 9 publications

(5 citation statements)

References 50 publications

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“…In recent years, some inexpensive and eco-friendly transition-metal-free organic reactions have gradually shown similar activity to transition metal catalysis. 9 Meanwhile, X–H (X = C, N, O, S) bond insertion reactions catalyzed by transition metals based on diazocarbene have also been reported. 10 As the new precursor of carbene, the diazo coupling reaction of α-aminoesters has attracted chemists’ attention in synthesis.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of α-aryl sulfides by deaminative coupling of α-amino compounds with thiophenols

et al. 2023

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Section: Introductionmentioning

confidence: 99%

Synthesis of α-aryl sulfides by deaminative coupling of α-amino compounds with thiophenols

et al. 2023

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“…Early examples include diazonium salts, , but these highly reactive intermediates prone to elimination typically lead to undesired side reactions and poor functional group tolerance. An interrupted diazotization strategy was recently leveraged to functionalize α-primary benzylamines with boronic acids . Benzylic ammonium salts have been coupled with boronic acids; however, the need for strongly alkylating agents potentially limits the scope of suitable substrates.…”

mentioning

confidence: 99%

“…An interrupted diazotization strategy was recently leveraged to functionalize α-primary benzylamines with boronic acids. 9 Benzylic ammonium salts have been coupled with boronic acids; 10 however, the need for strongly alkylating agents potentially limits the scope of suitable substrates. Katritzky-type pyridinium salts have been employed in several photocatalytic and metal-catalyzed cross-coupling reactions, affording a powerful platform to activate primary amines bearing moderate steric hindrance.…”

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confidence: 99%

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

et al. 2023

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While being among the most common functional handles present in organic molecules, amines are a widely underutilized linchpin for C–C bond formation. To facilitate C–N bond cleavage, large activating groups are typically used but result in the generation of stoichiometric amounts of organic waste. Herein, we report an atom-economical activation of benzylic primary amines relying on the sulfur(VI) fluoride exchange (SuFEx) click chemistry and the aza-Ramberg–Bäcklund reaction. This two-step sequence allows the high-yielding generation of 1,2-dialkyldiazenes from primary amines via loss of SO2. Excitation of the diazenes with blue light and an Ir photocatalyst afford radical pairs upon expulsion of N2, which can be coaxed into the formation of C(sp3)–C(sp2) bonds upon diffusion and capture by a Ni catalyst. This arylative strategy relying on a traceless click approach was harnessed in a variety of examples, and its mechanism was investigated.

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“…An interrupted diazotization strategy was recently leveraged to functionalize α-primary benzylamines with boronic acids. 9 Benzylic ammoniums salts have been coupled with boronic acids, 10 however the need for strongly alkylating agents potentially limits the scope of suitable substrates. Katritzky-type pyridinium salts have been employed in several photocatalytic and metal-catalyzed cross-coupling reactions, affording a powerful platform to activate primary amines bearing moderate steric hindrance.…”

mentioning

confidence: 99%

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

Chattapadhyay

Aydogan

Doktor

et al. 2023

Preprint

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While among the most common functional handles present in organic molecules, amines are a widely underutilized linchpin for C–C bond formation. To facilitate C–N bond cleavage, large activating groups are typically used but result in the generation of stoichiometric amounts of organic waste. Herein, we report an atom-economic activation of benzylic primary amines relying on the Sulfur Fluoride Exchange (SuFEx) click chemistry and the aza-Ramberg-Bäcklund reaction. This two-step sequence allows the efficient generation of 1,2-dialkyldiazenes from primary amines via loss of SO2. Excitation of the diazenes with blue light and an Ir photocatalyst affords radical pairs upon expulsion of N2, which can be coaxed into the formation of C(sp3)–C(sp2) bonds upon diffusion and capture by a Ni catalyst. This unique arylative strategy relying on a trace-less click approach was harnessed in a variety of examples and its mechanism was investigated.

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Deaminative coupling of benzylamines and arylboronic acids

Abstract: A metal-free deaminative coupling of non-prefunctionalised benzylamines and arylboronic acids is reported.

Cited by 9 publications

References 50 publications

Synthesis of α-aryl sulfides by deaminative coupling of α-amino compounds with thiophenols

Synthesis of α-aryl sulfides by deaminative coupling of α-amino compounds with thiophenols

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

Harnessing Sulfur(VI) Fluoride Exchange Click Chemistry and Photocatalysis for Deaminative Benzylic Arylation

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