Synthetic Exploration of Novel Sulfamoyl Cyanide <i>N</i>‐Oxides in Heterocycle Synthesis

Krivovicheva, Vasilisa; Bubyrev, Andrey; Kalinin, Stanislav; Dar’in, Dmitry; Krasavin, Mikhail

doi:10.1002/ejoc.202201162

Cited by 3 publications

(4 citation statements)

References 21 publications

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“…Their synthesis has been reported by Regitz 44 and more recently by Krasavin. 45 They have primarily been applied to a number of cycloaddition reactions and O-H insertions, [45][46][47][48][49][50][51][52][53][54] however, there are very few reports of their application to C-H insertions, despite a number of attempts principally by Yang and Xu and coworkers. [55][56][57][58] In a recent study, Yang and Xu investigated if aliphatic sp 3 C-H insertions were possible with a range of ester, methyl ketone and benzoyl substituted α-diazo-β-keto sulfonamides with rhodium and copper catalysts, however, 1,4-, 1,5-, or 1,6-C(sp 3 )-H insertion was not realised across a wide range of derivatives (Scheme 3, A).…”

Section: Scheme 2 Previous Work Within the Maguire Groupmentioning

confidence: 99%

Synthesis and Reactivity of α-Diazo-β-keto Sulfonamides

Collins,

Maguire,

Judge

et al. 2024

Synthesis

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Copper mediated reactions of α-diazo-β-keto sulfonamides 1 leads to a range of products including the alkyne sulfonamides 5, the enamines 6, and the α-halosulfonamides 7 and 11 with no evidence for intramolecular C–H insertion in any of the reactions, in contrast to the reactivity of the comparable α-diazo-β-keto sulfones. Use of copper(II) triflate (5 mol%) led to isolation of a series of alkyne sulfonamides 5 (up to 12%) and enamines 6 (up to 64%). Use of copper(II) chloride (5 mol%) formed, in addition, the α-halosulfonamides 7; use of stoichiometric amounts of copper(II) chloride/bromide enables facile halogenation of the β-keto sulfonamide to form the α-halosulfonamides 7 and 11 (up to 63%).

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Section: Scheme 2 Previous Work Within the Maguire Groupmentioning

confidence: 99%

Synthesis and Reactivity of α-Diazo-β-keto Sulfonamides

Collins,

Maguire,

Judge

et al. 2024

Synthesis

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“…It should be added that RCNO dimerization to furoxanes is not only a side reaction accompanying cycloaddition but also an important method of furoxane synthesis [ 156 , 296 ]. These compounds are attractive as pharmaceuticals [ 297 ] or even as explosive materials [ 298 ].…”

Section: Side Reaction Accompanying 13-dipolar Cycloadditionmentioning

confidence: 99%

Nitrile Oxide, Alkenes, Dipolar Cycloaddition, Isomerization and Metathesis Involved in the Syntheses of 2-Isoxazolines

et al. 2023

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The involvement of 1,3-dipolar cycloaddition (1,3-DP), double bond migration, metathesis, and nitrile oxide (including in situ-generated nitrile oxide) as dipoles, together with the C=C bond containing dipolarophiles, in the syntheses of 2-isoxazolines is presented. Methods for synthesizing isoxazolines (other than 1,3-DP cycloaddition) were also presented briefly. Various methods of nitrile oxide preparation, especially in situ-generated procedures, are presented. Special attention was paid to the application of various combinations of 1,3-DP cycloaddition with double bond migration (DBM) and with alkene metathesis (AM) in the syntheses of trisubstituted isoxazolines. Allyl compounds of the type QCH2CH=CH2 (Q = ArO, ArS, Ar, and others) play the role of dipolarophile precursors in the combinations of DPC mentioned, DBM and AM. Mechanistic aspects of cycloadditions, i.e., concerted or stepwise reaction mechanism and their regio- and stereoselectivity are also discussed from experimental and theoretical points of view. Side reactions accompanying cycloaddition, especially nitrile oxide dimerization, are considered. 2-Isoxazoline applications in organic synthesis and their biological activity, broad utility in medicine, agriculture, and other fields were also raised. Some remaining challenges in the field of 1,3-DP cycloaddition in the syntheses of isoxazolines are finally discussed.

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“…Since the use of diversely substituted CÀ H diazomethane sulfonamides 1 had been already optimized for various cycloaddition events, [13][14][15][16][17][18] we relied on those conditions in exploring the syntheses of heterocyclic, azole-based primary sulfonamides with the use of newly designed reagent 2.…”

Section: Chemmedchemmentioning

confidence: 99%

“…Recently, we introduced a new class of diazo compoundsnamely, N,N-disubstituted CÀ H diazomethane sulfonamides 1 which proved to be useful building blocks in the synthesis of such aromatic five-membered nitrogen heterocycles as pyrazoles, [13][14] tetrazoles, [15] 1,2,3-triazoles [16][17] and isoxazoles. [18] We reasoned that if we prepared a special version of CÀ H diazomethane sulfonamide 2 where the two substituents on the sulfonamide nitrogen atom were easily removable protecting groups, this would not only open an entry into the chemical space of primary azole sulfonamides but also provide a flexible and medicinal chemistry friendly way to vary the molecular periphery around the azole scaffold in order to optimize the potency and selectivity of inhibition of specific carbonic anhydrase isoforms. As a candidate protecting group we chose p-methoxybenzyl (PMB) which proved to provide a convenient protection of sulfonamide moieties (Figure 2).…”

Section: Introductionmentioning

confidence: 99%

Versatile Diazomethane Sulfonamide for Expedited Exploration of Azole‐Based Carbonic Anhydrase Inhibitors via [3+2] Cycloaddition

et al. 2023

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A newly introduced diazo reagent, 1‐diazo‐N,N‐bis(4‐methoxybenzyl)methanesulfonamide, enables access to a range of azole‐based primary sulfonamides via [3+2] cycloaddition followed by protecting group removal. Such compounds are representative of the sulfonamide chemical space highly relevant but hitherto not investigated in the context of inhibition of therapeutically relevant isoforms of carbonic anhydrase enzyme. Using this reagent, three sets of primary sulfonamides based on pyrazole, 1,2,3‐triazole and tetrazole cores were synthesized and profiled for inhibition of tumor‐associated hCA IX and XII isoforms as well as abundant cytosolic hCA I and II isoforms. Using virtual library design and docking prioritization tool of the Schrödinger suite, one of the promising leads was evolved into a dual hCA IX/XII inhibitor with excellent selectivity over off‐target hCA I and II. The new synthetic strategy to access azole‐based primary sulfonamides will support the discovery of novel, isoform‐selective inhibitors of carbonic anhydrase within the poorly explored azole chemical space.

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Synthetic Exploration of Novel Sulfamoyl Cyanide N‐Oxides in Heterocycle Synthesis

Cited by 3 publications

References 21 publications

Synthesis and Reactivity of α-Diazo-β-keto Sulfonamides

Synthesis and Reactivity of α-Diazo-β-keto Sulfonamides

Nitrile Oxide, Alkenes, Dipolar Cycloaddition, Isomerization and Metathesis Involved in the Syntheses of 2-Isoxazolines

Versatile Diazomethane Sulfonamide for Expedited Exploration of Azole‐Based Carbonic Anhydrase Inhibitors via [3+2] Cycloaddition

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