Sulfonyl Hydrazines Research Articles

Organocatalytic synthesis of 5-hydroxyisoxazolidine catalyzed by camphor sulfonyl hydrazines through aza-Michael addition/cyclization.

A series of chiral 5-hydroxy isoxazolidines has been successfully synthesized through camphor sulfonyl hydrazine-catalyzed asymmetric aza-Michael addition reaction between N,O-protected hydroxyamines and enals. Moderate yields with moderate to good enantioselectivities (up to 96% enantiomeric excess [ee]) were achieved. It provides an alternative asymmetric approach to preparing isoxazolidine derivatives.

Synthesis of 3-Alkylthiol Pyrazoles via Regioselective Annulation Reactions of Sulfonyl Hydrazines and Ketene Dithioacetals

Synthesis of 3-Alkylthiol Pyrazoles via Regioselective Annulation Reactions of Sulfonyl Hydrazines and Ketene Dithioacetals

Recent Advances in the Synthesis of Thiadiazoles

Thiadiazole moieties are present in many natural products and pharmaceutical compounds that possess a broad spectrum of biological activities, serving as antidepressant, anxiolytic, antimicrobial, antitubercular, antiinflammatory, antidiabetic, anticancer, antihypertensive, or antifungal drugs. Many excellent methods have been reported for accessing such frameworks. In this review, we summarize advances made within the past ten years in the synthesis of various types of thiadiazole.1 Introduction2 Synthesis of Thiadiazoles2.1 Synthesis of 1,2,3-Thiadiazoles2.1.1 Synthesis of 1,2,3-Thiadiazoles from Diazo/Azide Compounds2.1.2 Synthesis of 1,2,3-Thiadiazoles from Sulfonyl Hydrazines or N-Tosylhydrazones2.2 Synthesis of 1,2,4-Thiadiazoles2.2.1 Synthesis of 1,2,4-Thiadiazoles from Thioamides or their Derivatives2.2.2 Synthesis of 1,2,4-Thiadiazoles from Amidines or 2-Aminopyridines2.3 Synthesis of 1,3,4-Thiadiazoles2.4 Synthesis of 1,2,5-Thiadiazoles3 Conclusion

Visible-Light-Mediated Tandem Sulfonylation/Cyclization of Vinyl Azides with Sulfonyl Hydrazines for the Synthesis of 6-(Sulfonylmethyl)phenanthridines under Mild Conditions

A visible-light-mediated tandem sulfonylation/cyclization of vinyl azides with sulfonyl hydrazines was developed that provides an efficient and simple strategy for the synthesis of valuable 6-(sulfonylmethyl)phenanthridines with a broad substrate scope and satisfactory yields under mild conditions.

Domino C-H Sulfonylation and Pyrazole Annulation for Fully Substituted Pyrazole Synthesis in Water Using Hydrophilic Enaminones

The cascade reactions between NH2-functionalized enaminones and sulfonyl hydrazines have been developed for the synthesis of fully substituted pyrazoles. By making use of the hydrophilic primary amino group in the enaminones, the reactions proceed well in the medium of pure water in the presence of molecular iodine, TBHP, and NaHCO3 via cascade C-H sulfonylation and pyrazole annulation. The cleavage of the C-N bond in enaminones is confirmed by the experiment using 15 N-labeled enaminone.

TBN-mediated regio- and stereoselective sulfonylation & oximation (oximosulfonylation) of alkynes with sulfonyl hydrazines in EtOH/H2O

A difunctionalization of alkynes cascade reaction was developed to generate α-sulfonylethanone oximes in environmentally benign EtOH/H2O.

Organocatalytic asymmetric Michael addition between 3-subsituted oxindoles and enals catalyzed by camphor sulfonyl hydrazine.

Organocatalytic asymmetric Michael addition between 3-substituted oxindoles and enals catalyzed by chiral camphor sulfonyl hydrazines (CaSHs) has been developed. A wide range of 3-substituted oxindoles and enals were successfully used, giving the corresponding 3,3-disubstituted oxindoles containing vicinal stereogenic carbon centers in good yields with good to excellent enantioselectivities and moderate to good diastereoselectivities (up to 89% yield, 99% ee and 99 : 1 dr).

Direct Synthesis of Benzo[ f]indazoles from Sulfonyl Hydrazines and 1,3-Enynes by Copper-Catalyzed Annulation.

A novel and efficient strategy for the direct synthesis of benzo[ f]indazoles via copper-catalyzed cascade reaction of sulfonyl hydrazides with 1,3-enynes under mild conditions has been developed. This method achieves the formation of two C-N bonds and one C-C bond in one pot, providing a series of benzo[ f]indazoles in moderate to good yields with good functional group tolerance and remarkable regioselectivity.

Electrochemical Oxidative Alkoxysulfonylation of Alkenes Using Sulfonyl Hydrazines and Alcohols with Hydrogen Evolution

An electrochemical oxidative alkoxysulfonylation of alkenes using sulfonyl hydrazines with alcohols is accomplished, which leads to the easy accessibility of β-alkoxy sulfones, which are not only valuable architectures of many biologically active molecules, but also key building blocks for various organic transformations. Notably, for this efficient electrochemical synthesis protocol, neither metal catalysts nor exogenous additives/oxidants are required. In addition, molecular nitrogen and hydrogen were the sole byproducts in the reaction.

Transition-metal-free synthesis of 3-sulfenylated chromones via KIO3-catalyzed radical C(sp2)-H sulfenylation.

The reactions between o-hydroxylphenyl-functionalized enaminones and sulfonyl hydrazines providing 3-sulfenylated chromones via domino chromone ring construction and C(sp2)–H bond sulfenylation have been achieved under transition-metal-free conditions by using KIO3 as the only catalyst.

KI as iodine source for the synthesis of E-iodovinyl sulfones via metal-free iodosulfonylation of terminal alkynes

GRAPHICAL ABSTRACT

Iodine‐Mediated Domino C(sp2)–H Sulfonylation/Annulation of Enaminones and Sulfonyl Hydrazines for the Synthesis of 3‐Sulfonyl Chromones

Radical C(sp2)–H sulfonylation and C(sp2)–N bond oxygenation enabling the chemoselective synthesis of 3‐sulfonyl chromones by using enaminones and sulfonyl hydrazines were accomplished. The domino reactions ran well by using molecular iodine without the assistance of any strong oxidant such as a peroxide or a hypervalent metal salt.

Water-acetic acid mediated chemoselective synthesis of pyrazolines via multimolecular domino reactions of enaminones and sulfonyl hydrazines

The domino reactions between enaminones and sulfonyl hydrazines enabling novel synthesis of pyrazoline have been achieved by employing water as reaction medium and acetic acid as cheap and green additive are reported. Two new CN and one new CN bonds have been constructed during the formation of these pyrazoline scaffolds. Unlike the conventional formation of pyrazoles in the organic solvent mediated reactions of enaminones and hydrazines, the present reactions providing pyrazolines disclose new transformation pattern of enaminones by employing water as medium.

KI-mediated radical multi-functionalization of vinyl azides: a one-pot and efficient approach to β-keto sulfones and α-halo-β-keto sulfones

Transition metal-free oxidative coupling of vinyl azides with sulfonyl hydrazines is described.

Identification of compounds that contribute to trigeminal burn in aqueous ethanol solutions

The influence of carbonyl species on the trigeminal burn of distilled spirit model systems was investigated. Quantities of the intrinsic carbonyl compounds were significantly altered in 40% ethanol solutions using two methods; (1) increasing or decreasing the product pH, to induce hemiacetal formation and acetal stabilization or induce and stabilize carbonyl species such as aldehydes, respectively and (2) utilizing a sulfonyl hydrazine polymer treatment. Samples with reduced carbonyl concentrations had significantly lower perceived trigeminal burn intensity. Sensory recombination experiments revealed that addition of carbonyl compounds increased trigeminal burn perception in model systems; confirming the direct relationship between the concentration of carbonyl compounds and trigeminal burn. The strongest potentiators of the trigeminal response were carbonyl compounds octanal, nonanal, benzaldehyde and 2-heptanone suggesting the probability that carbonyl species such as saturated aldehydes and ketones act as agonists to activate nociceptors such as TRPV1 and TRPA1 and elicit trigeminal burn.

ChemInform Abstract: Ultrasound‐Assisted, Convenient and Widely Applicable 1,1′‐Carbonyl‐diimidazole‐Mediated “One‐Pot” Synthesis of Acyl/Sulfonyl Hydrazines.

AbstractA diverse range of benzoic and sulfonic acid derivatives including biologically and pharmaceutically relevant ones are efficiently transformed into acyl and sulfonyl hydrazines.

Synthesis of Several New Schiff Bases Linked to Sulfonamido Naphthalimide Moiety with Expected Biological Activity.

Several new Schiff bases linked to sulfonamidonaphthalimide moiety have been synthesized. The first step in this work involved introducing of 4-(N-naphthalimidyl) phenyl sulfonylchloride in amination reaction with hydrazine hydrate producing 4-(N-naphthalimidyl) phenyl sulfonylhydrazine. Introducing of the prepared sulfonyl hydrazine in condensation reaction with different substituted aromatic aldehydes in the second step afforded the target new Schiff bases. Structures of the prepared compounds were elucidated on the basis of FTIR, 1HNMR, 13CNMR spectral data which agreed with the proposed structures. The newly synthesized compounds are expected to have biological activity scince they are built from biologically active components including naphthalimide, sulfonylimide and Schiff base.

Ionic liquid-supported sulfonyl hydrazine: a useful reagent for traceless synthesis of pyrazoles

Ionic liquid-supported sulfonyl hydrazine has been synthesized and used as a soluble support for the traceless synthesis of highly substituted pyrazoles from two different routes. Various substituted pyrazoles were synthesized in high yields. A key feature of the protocol is an easy and convenient purification process that avoids chromatographic separation of products and thus makes the method eco-friendly and economical.

ChemInform Abstract: Regioselective Hydrothiolation of Alkynes by Sulfonyl Hydrazines Using Organic Ionic Base—Broensted Acid.

AbstractNotable advantages of the novel title method are the use of sulfonyl hydrazides as thiol equivalents, excellent regioselectivity, short reaction times, and the use of a recyclable ionic liquid.

Sulfonyl hydrazine-functionalized polymer as a specific capturer of reducing glycans from complex samples for high-throughput analysis by electrospray ionization mass spectrometry

Qualitative and quantitative studies of glycosylation patterns of various biologically important proteins represent a key field for the understanding of their complex structure-function relationships. However, the analysis of glycoprotein glycans is usually undermined by tedious sample processing steps prior to detection, including deproteination, desalting and removal of some other non-glycan impurities, which results in considerable sample loss and increased difficulty of quantitative analysis. Herein we report a facile and versatile method for the quantitative isolation of reducing glycans from complex samples using sulfonyl hydrazine-functionalized polystyrene (SHPS) beads, namely the SHPS-based glycan capturing procedure. This method allows the chemoselective and efficient condensation of the aldehyde group of reducing glycans with the active sulfonyl hydrazine group of SHPS beads under anhydrous conditions, resulting in the formation of sulfonyl hydrazone conjugates. The non-glycan components in samples, such as proteins, salts and some other impurities, can be completely removed by washing the sulfonyl hydrazone conjugates. Regeneration of the reducing glycans can be performed via mild hydrolysis of the washed sulfonyl hydrazone conjugates. This procedure is compatible with almost all the current techniques for the derivatization or detection of reducing glycans. We have obtained essential data for this method, including optimized reaction conditions, linearity and reproducibility for glycan quantitation, as well as a final glycan recovery ratio. Moreover, mass spectrometric analysis of the glycans from some complex biological samples, including milk, human blood plasma and fetal bovine serum, was achieved, demonstrating good applicability of this novel procedure.