Isothiocyanates: happy-go-lucky reagents in organic synthesis.

Owing to their unique structural features, isothiocyanates (ITCs) are a class of highly useful and inimitable reagents as the -NCS group serves both as electrophile and nucleophile in organic synthesis. ITCs share a rich legacy in organic, medicinal, and combinatorial chemistry. Compared to their oxygen equivalents, isocyanates, ITCs are easily available, less unpleasant, and somewhat less harmful to work with (mild conditions) which makes them happy-go-lucky reagents.

Synthesis of Chromenopyrroles (Azacoumestans) from Functionalized Enones and Alkyl Isocyanoacetates.

Elegant synthetic strategies for chromenopyrroles (azacoumestans) have been devised via cycloaddition of 2-hydroxychalcone/cyclic enones and alkyl isocyanoacetate, followed by lactonization. Herein, ethyl isocyanoacetate acts as a C-NH-C-C═O synthon contrary to its hitherto applications as a C-NH-C synthon. Subsequently, pentacyclic-fused pyrroles were also constructed from the -iodo benzoyl chromenopyrroles using the Pd(II) catalyst.

NIS-initiated photo-induced oxidative decarboxylative sulfoximidation of cinnamic acids.

-Iodosuccinimide catalyzed, visible-light-induced oxidative decarboxylative cross-coupling between cinnamic acids and NH-sulfoximines is presented. This strategy results in the formation of α-keto--acyl sulfoximines the construction of two new CO bonds and one C-N bond. The -generated -iodosulfoximine serves as the light-absorbing species in the absence of any external photosensitizer.

Transformable Transient Directing Group-Assisted C(sp)-H Activation: Synthesis and Late-Stage Functionalizations of -Alkenylanilines.

The isocyanate group in aryl isocyanates serves as a transformable transient directing group in a Ru(II)-catalyzed olefination leading to -alkenylanilines. In alcoholic solvents, aryl isocyanates are transformed into carbamates, which initiate the insertion of acrylates via -C-H activation. In particular, AmOH serves the dual role of solvent-cum transient directing mediator.

Visible-Light-Mediated Synthesis of Thio-Functionalized Pyrroles.

An inimitable illustration of the green-light-induced synthesis of thio-functionalized pyrroles has been established using β-ketodinitriles and thiophenols as the reacting partners and eosin Y as the photocatalyst. Large-scale synthesis and some useful synthetic modifications of the thio-functionalized pyrroles are also demonstrated.

Correction: Updates on hypervalent-iodine reagents: metal-free functionalisation of alkenes, alkynes and heterocycles.

Correction for 'Updates on hypervalent-iodine reagents: metal-free functionalisation of alkenes, alkynes and heterocycles' by Anjali Dahiya , , 2022, DOI: 10.1039/d1ob02233d.

Updates on hypervalent-iodine reagents: metal-free functionalisation of alkenes, alkynes and heterocycles.

Hypervalent iodine (HVI) chemistry is a rapidly growing subdomain of contemporary organic chemistry because of its enormous synthetic applications. The high nucleofugality of the phenyliodonio group (-IPh) and its radical nature, serving as a single-electron oxidant makes HVI compounds highly valuable in organic synthesis. Due to the feasibility and benignity, reactions that rely solely on HVI reagents as promoters have received particular interest.

Cu(II)-Promoted Cascade Synthesis of Fused Imidazo-Pyridine-Carbonitriles.

A Cu(II)-promoted synthesis of an aza-fused N-heterocycle having a benz-imidazopyridine scaffold is developed via an addition-cyclization reaction followed by an Ullmann-type C-N coupling between -iodoanilines and -ketodinitriles. This protocol features a broad substrate scope, giving products in 32-84% yields. The compounds show excellent photoluminescence properties having two absorption maxima in the region between 270-280 and 338-350 nm and emission maxima in the range of 502-533 nm.

Visible-Light-Mediated Difunctionalization of Alkynes: Synthesis of β-Substituted Vinylsulfones Using - and -Centered Nucleophiles.

An inimitable illustration of a green-light-induced, regioselective difunctionalization of terminal alkynes has been disclosed using sodium arylsulfinates and carboxylic acids in the presence of eosin Y as the photocatalyst. The present methodology is further demonstrated by employing NHSCN as an -centered nucleophile instead of carboxylic acid. The mechanistic investigation reveals a radical-induced iodosulfonylation followed by a base-mediated nucleophilic substitution.

An expedient route to tricyanovinylindoles and indolylmaleimides from o-alkynylanilines utilising DMSO as a one-carbon synthon.

A Pd(ii)/Cu(ii) catalysed domino synthesis of tricyanovinylindoles has been achieved using DMSO as a one-carbon synthon. The reaction proceeds via the construction of 2-aryl-3-formyl indole followed by sequential addition of malononitrile and a CN resulting in two C-C, one C[double bond, length as m-dash]C and one C-N bonds in the final product. Furthermore, post-synthetic modification results in the unprecedented formation of 4-cyano-3-indolylmaleimides.

The Rich Legacy and Bright Future of Transition-Metal Catalyzed Peroxide Based Radical Reactions.

This personal account is mainly focused on the author's involvement in the field of transition metal-catalyzed peroxide based radical reactions. Over the past decades, radical chemistry has flourished and become crucial in contemporary synthetic organic chemistry. Owing to the presence of a single electron in one orbital, radicals are very unstable and react very fast.

Kaempferol-zinc(II) complex synthesis and evaluation of bone formation using zebrafish model.

Flavonoids are known for their wide range of bioactive properties including beneficial effect on bone formation. Their intense metal ion chelating capacity endorsed their nomination as a new biomaterial for biomedical applications. The present study examined the functional role of Kaemferal-Zinc(II) (Kaem-Zn) complex in bone formation, in vitro and in vivo.

Visible-Light-Induced Difunctionalization of Styrenes: Synthesis of -Hydroxybenzimidoyl Cyanides.

A visible-light-induced synthesis of -hydroxybenzimidoyl cyanides from aromatic terminal alkenes is achieved by using Eosin Y as an organic photoredox catalyst. The process goes via a radical pathway with successive incorporation of two nitrogen atoms, one each from -butyl nitrite and ammonium acetate. The final product is achieved by the concomitant installation of an oxime and a nitrile group.

tert-Butyl Nitrite (TBN), a Multitasking Reagent in Organic Synthesis.

The upsurge interest in the development of efficient methodologies for the construction of nitrogen-containing frameworks via the use of expedient reagents have been creating a renaissance in contemporary organic chemistry. In this perspective, tertbutyl nitrite (TBN) is an emerging building block. Due to its unique structural features, it shows differential reactivity under different reaction conditions.

A cascade synthesis of S-allyl benzoylcarbamothioates via Mumm-type rearrangement.

A catalyst and solvent free synthesis of S-allyl benzoylcarbamothioates has been achieved from the in situ generated benzoylcarbonimidothioates obtained by reacting MBH alcohols with aroyl isothiocyanates. An intramolecular thia-Michael addition of the in situ generated adduct triggers a Mumm-type rearrangement leading to a stereoselective synthesis of highly functionalised S-allyl benzoylcarbamothioates.

Microwave-Assisted Cascade Strategy for the Synthesis of Indolo[2,3-b]quinolines from 2-(Phenylethynyl)anilines and Aryl Isothiocynates.

The in situ generated o-alkynylthioureas obtain by reacting 2-(phenylethynyl)anilines and aryl isothiocynates undergo efficient cascade cyclization in the presence of AgCO to form indoloquinolines under microwave heating. The present tandem process allows the generation of a variety of indolo[2,3-b]quinolines derivatives in good to moderate yields with a wide functional group tolerance.

Cutaneous manifestation of disseminated strongyloidiasis in a patient coinfected with HTLV-I.

Strongyloidiasis is a potentially lethal parasitic infection. Coinfection of a patient with human T-lymphotropic virus type I (HTLV-I) can lead to a more severe disease course and treatment-refractoriness. Here we report a patient coinfected with HTLV-I and Strongyloides stercoralis who developed disseminated, treatment-resistant disease.