Process-Controlled Regiodivergent Copper-Catalyzed Azide–Alkyne Cycloadditions: Tailor-made Syntheses of 4- and 5-Bromotriazoles from Bromo(phosphoryl)ethyne

Okuda, Yasuhiro; Imafuku, Kazuto; Tsuchida, Yoshiyuki; Seo, Tomoyo; Akashi, Hidetoshi; Orita, Akihiro

doi:10.1021/acs.orglett.0c01681

Cited by 11 publications

(16 citation statements)

References 28 publications

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“…Starting material thiols 1 were purchased from Energy, Sigma-Aldrich, and Leyan. Starting material 2 was synthesized according to the reported procedure …”

Section: Methodsmentioning

confidence: 99%

Process-Divergent Syntheses of 4- and 5-Sulfur-Functionalized 1,2,3-Triazoles via Copper-Catalyzed Azide–Alkyne Cycloadditions of 1-Phosphinyl-2-sulfanylethynes

et al. 2023

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4-Sulfanyl-substituted 1,2,3-triazoles were provided regioselectively with good yields and broad scope via consecutive t-BuOK-promoted dephosphinylation of 1-phosphinyl-2-sulfanylethynes and copper-catalyzed azide–alkyne cycloadditions (CuAAC) with alkyl azides. Unsymmetrically substituted ditriazoles were successfully obtained using a tandem dephosphinylative CuAAC protocol with diazides. Direct CuAAC of the 1-phosphinyl-2-sulfanylethynes with azides afforded regioisomeric mixtures of 4-phosphinyl-5-sulfanyl- and 5-phosphinyl-4-sulfanyl-1,2,3-triazoles that were easily separable from one another. When the phosphinyl- and sulfanyl-substituted triazoles were treated with t-BuOK, the dephosphination proceeded smoothly, yielding the corresponding 5- and 4-sulfanyltriazoles, respectively. 5-(1-Aryl-1-hydroxymethyl)-4-sulfanyltriazoles were synthesized by stepwise treatment of 5-phosphinyl-4-sulfanyltriazole with MeMgBr and arylaldehydes. Additionally, Ph2P(O) and RS groups in the triazoles were easily converted to Ph2P and RSO2 by PhSiH3-reduction and m-CPBA-oxidation, respectively. Following the dephosphinylative CuAAC of 1-phosphinyl-2-(4-t-butylphenylsulfanyl)ethyne with aryl azides and m-CPBA-oxidation, potent antagonists of pregnane X receptor LC-58 and LC-59 were successfully produced.

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“…Starting material thiols 1 were purchased from Energy, Sigma-Aldrich, and Leyan. Starting material 2 was synthesized according to the reported procedure …”

Section: Methodsmentioning

confidence: 99%

Process-Divergent Syntheses of 4- and 5-Sulfur-Functionalized 1,2,3-Triazoles via Copper-Catalyzed Azide–Alkyne Cycloadditions of 1-Phosphinyl-2-sulfanylethynes

et al. 2023

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“…CuI-Catalyzed Synthesis. Orita and co-workers 53 reported a process-controlled regiodivergent copper-catalyzed process for the synthesis of 4-bromo-and 5-bromotriazoles 6 and 7 through cycloaddition between bromo(phosphoryl)ethyne 5 and azide 2 using CuI as a catalyst and MeOH/H 2 O as a proton source for regeneration of the copper catalyst (Scheme 3). KOH-promoted one-shot dephosphorylation of 5 with azide resulted in 4-bromo-1,2,3-triazole 6.…”

Section: Synthesis Of 123-triazole Via Metal-catalyzed Azide−alkyne C...mentioning

confidence: 99%

Versatile Synthetic Platform for 1,2,3-Triazole Chemistry

Vala

Patel

2022

ACS Omega

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1,2,3-Triazole scaffolds are not obtained in nature, but they are still intensely investigated by synthetic chemists in various fields due to their excellent properties and green synthetic routes. This review will provide a library of all synthetic routes used in the past 21 years to synthesize 1,2,3-triazoles and their derivatives using various metal catalysts (such as Cu, Ni, Ru, Ir, Rh, Pd, Au, Ag, Zn, and Sm), organocatalysts, metal-free as well as solvent- and catalyst-free neat syntheses, along with their mechanistic cycles, recyclability studies, solvent systems, and reaction condition effects on regioselectivity. Constant developments indicate that 1,2,3-triazoles will help lead to future organic synthesis and are useful for creating molecular libraries of various functionalized 1,2,3-triazoles.

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“…The corresponding triazoles were obtained in very high regioselectivities, up to 99 % (Scheme 32). [50] …”

Section: The Synthesis Of 5 and 4‐halo‐123‐triazoles By [3+2] Cycloadditionmentioning

confidence: 99%

An Overview of 4‐ and 5‐Halo‐1,2,3‐triazoles from Cycloaddition Reactions

Arenas

Crousse

2021

Eur J Org Chem

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1,2,3‐triazoles are important scaffolds in several fields, and there is still a demand to construct these compounds, most notably the disubstituted 4, 5 compounds. The latter are obtained in different ways, but the 4‐ and 5‐halo triazoles are generally the key intermediates in their synthesis. These halogenated compounds are an extraordinary platform leading to a great chemical diversity around the 4 and 5 positions. However, their own pathways are generally put aside at the expense of the substituted triazoles. This review is focused on the main synthesis of 5‐ and 4‐halo 1,2,3‐triazoles from cycloaddition followed or not by halogenation reaction. Unlike the halogens (iodine, bromine, and chlorine), the 5‐ and 4‐fluoro 1,2,3‐triazoles will be presented separately due to their relatively more difficult and still recently challenging synthesis.

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Process-Controlled Regiodivergent Copper-Catalyzed Azide–Alkyne Cycloadditions: Tailor-made Syntheses of 4- and 5-Bromotriazoles from Bromo(phosphoryl)ethyne

Cited by 11 publications

References 28 publications

Process-Divergent Syntheses of 4- and 5-Sulfur-Functionalized 1,2,3-Triazoles via Copper-Catalyzed Azide–Alkyne Cycloadditions of 1-Phosphinyl-2-sulfanylethynes

Process-Divergent Syntheses of 4- and 5-Sulfur-Functionalized 1,2,3-Triazoles via Copper-Catalyzed Azide–Alkyne Cycloadditions of 1-Phosphinyl-2-sulfanylethynes

Versatile Synthetic Platform for 1,2,3-Triazole Chemistry

An Overview of 4‐ and 5‐Halo‐1,2,3‐triazoles from Cycloaddition Reactions

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