Trivalent Organostibines: Sb,N Ligands in Double N-Arylation of Primary Amines toward Functionalized Carbazoles.

A Sb,N ligand (L-Sb) for Pd-catalyzed double N-arylation of primary amines was developed. This trivalent ligand L-Sb, containing a 5,6,7,12-tetrahydrodibenzo[c,f][1,5]azastibocine skeleton and stable under air and moisture, could be synthesized facilely on a gram scale from chlorostibine (1) and cyclopentylmagnesium bromide. L-Sb showed excellent catalytic performance in Pd2(dba)3-catalyzed double N-arylation of 2,2'-dibromo-1,1'-biphenyl (2) with primary amines (3), affording functionalized carbazoles in good yields. This Pd2(dba)3/L-Sb-catalyzed double N-arylation, the first example of the application of trivalent organostibines as a ligand in N-arylation, featured the following advantages: small catalyst loading, wide functional group tolerance, good yields, and ease of gram-scale synthesis.

Nickel-Catalyzed C(sp3)-Sb Coupling of Chlorostibines with Unactivated Alkyl Chlorides and In Vitro Anticancer Activity of Products.

In this study, we present a nickel-catalyzed reductive C(sp3)-Sb coupling of unactivated alkyl chlorides with chlorostibines. This approach is highly versatile, tolerating various functional groups such as acetal, alkene, nitrile, amine, ester, silyl ether, thioether, and various heterocyclic compounds. Notably, the late-stage modification of bioactive molecules and the satisfactory anticancer activity against cancerous MDA-MB-231 also demonstrate the potential application.

Recent Progress on Nitrogen-Rich Energetic Materials Based on Tetrazole Skeleton.

Development of nitrogen-rich energetic materials has gained much attention because of their remarkable properties including large nitrogen content and energy density, good thermal stability, low sensitivity, good energetic performance, environmental friendliness and so on. Tetrazole has the highest nitrogen and highest energy contents among the stable azoles. The incorporation of diverse explosophoric groups or substituents into the tetrazole skeleton is beneficial to obtain high-nitrogen energetic materials having excellent energetic performance and suitable sensitivity. In this review, the development of high-nitrogen energetic materials based on tetrazole skeleton is highlighted. Initially, the property and utilization of nitrogen-rich energetic materials are presented. After showing the advantage of the tetrazole skeleton, the high-nitrogen energetic materials based on tetrazole are classified and introduced in detail. Based on different types of energetic materials (EMs), the synthesis and properties of nitrogen-rich energetic materials based on mono-, di-, tri- and tetra-tetrazole are summarized in detail.

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

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.

Selectfluor-Promoted Reactions of Aryl Methyl Ketones with Dimethyl Sulfoxide to Give 2,5-Diacylthiophenes and ß-Acyl Allylic Methylsulfones.

In this paper, a convenient synthesis of 2,5-diacylthiophenes and ß-acyl allylic methylsulfones from aryl methyl ketones with dimethyl sulfoxide (DMSO) through Selectfluor-promoted cascade cyclization and cross-coupling reactions by simple solvent modification is described. This method enables the formation of new C-C and C-S bonds via the selection of different solvent ratios, in which DMSO molecules as synthons can be selectively introduced into methyl ketones. The features of this transformation include readily available starting materials, excellent chemoselectivity, and good functional group tolerance.

Copper-Catalyzed Cyclization of 2-Alkynylanilines to Give 2-Haloalkoxy-3-alkyl(aryl)quinolines.

Herein we describe a method to produce 2-haloalkoxy-3-substituted quinolines via the cyclization of 2-alkynylanilines with TMSCF3 and THF. This synthetic method uses inexpensive and easy-to-handle TMSCF3 and employs a commercially available CuI catalyst to transform a broad range of 2-alkynylanilines into versatile 2-difluoromethoxy-3-substituted quinolines and 2-iodoalkoxy-3-substituted quinolines with excellent chemoselectivity.

DTBP-mediated cross-dehydrogenative coupling of 3-aryl benzofuran-2(3H)-ones with toluenes/phenols for all-carbon quaternary centers.

We have developed a transition-metal free protocol for efficient cross-dehydrogenative coupling of 3-aryl benzofuran-2(3H)-ones and toluenes/phenols using DTBP as an oxidant. A diverse range of 3-aryl benzofuran-2(3H)-ones, toluenes, and phenols undergo C-H bond cleavage to generate all-carbon quaternary centers in good yields, making this protocol useful for the synthesis of complex molecules. A gram scale experiment was performed in good yield.

Co-Catalyzed Dual C5/C8-H Bond Functionalization of Imidazo[1,2-a]pyrazines with Disulfides and Grignard Reagents.

An efficient difunctionalization at C5/C8 of imidazo[1,2-a]pyrazines has been developed using disulfides and Grignard reagents under cheap cobalt catalysis. This one-pot, two-step, three-component transformation is performed under mild conditions; various Grignard reagents (aryl and alkyl) and disulfides are tolerated. Mechanistic studies and control experiments demonstrate this reaction proceeded via an anionic intermediate.

Recent Advances in the Use of Dimethyl Sulfoxide as a Synthon in Organic Chemistry.

Dimethyl sulfoxide (DMSO), as extremely important aprotic polar solvent and reaction medium, has attracted widespread attention from chemists in recent years due to its wide range of uses and the multiple functions it displays in various chemical processes. Especially in the past decade, dimethyl sulfoxide has become increasingly favored as a synthon in organic chemistry, resulting in great progress in this research field. In this context, this review provides a comprehensive summary of the literature on the recent progress in organic synthesis using dimethyl sulfoxide as a synthon, covering all the reports from 1 January 2016 to 11 May 2022. This type of reaction is mainly performed by transferring one or more units of dimethyl sulfoxide, such as oxygen (-O-, =O), methyl (-CH3), methylene (-CH2-), methylidene (=CH2), methine (=CH-), donor of formylation (-CHO), sulfur (-S-), methylthio (-SMe), methyl sulfoxide (-SOMe), donor of methyl thiomethylation (-CH2SMe), or donor of methyl sulfoxide methylation (-CH2SOMe), to the target molecules. At the same time, we hope that this review will stimulate future studies and promote developments in this area.

Copper-Catalyzed Regioselective Iodoformylation of Terminal Alkynes to Access Versatile Electrophiles (E)-ß-Iodo-α,ß-Unsaturated Aldehydes.

Herein, we describe a method for synthesizing (E)-ß-iodo-α,ß-unsaturated aldehydes via the iodoformylation of terminal alkynes with TMSCF3 and NaI. This synthetic method uses inexpensive and easy-to-handle chemical feedstocks and employs a commercially available CuI catalyst. It can transform a broad range of terminal alkynes into bis-electrophile (E)-ß-iodo-α,ß-unsaturated aldehydes with excellent chemoselectivity, regioselectivity, and stereoselectivity. Moreover, it was demonstrated that this protocol has abundant organic reactivity.

Zirconium-Based Catalysts in Organic Synthesis.

Zirconium is a silvery-white malleable and ductile metal at room temperature with a crustal abundance of 162 ppm. Its compounds, showing Lewis acidic behavior and high catalytic performance, have been recognized as a relatively cheap, low-toxicity, stable, green, and efficient catalysts for various important organic transformations. Commercially available inorganic zirconium chloride was widely applied as a catalyst to accelerate amination, Michael addition, and oxidation reactions. Well-designed zirconocene perfluorosulfonates can be applied in allylation, acylation, esterification, etc. N-Chelating oganozirconium complexes accelerate polymerization, hydroaminoalkylation, and CO2 fixation efficiently. In this review, the applications of both commercially available and synthesized zirconium catalysts in organic reactions in the last 5 years are highlighted. Firstly, the properties and application of zirconium and its compounds are simply introduced. After presenting the superiority of zirconium compounds, their applications as catalysts to accelerate organic transformations are classified and presented in detail. On the basis of different kinds of zirconium catalysts, organic reactions accelerated by inorganic zirconium catalysts, zirconium catalysts bearing Cp, and organozirconium catalysts without Cp are summarized, and the plausible reaction mechanisms are presented if available.

Base-Promoted Reactions of Organostibines with Alkynes and Organic Halides to Give Chalcogenated (Z)-Olefins and Ethers.

Herein, with air-stable chalcogenated stibines (Sb-ER) as organometallic chalcogenating reagents, we developed base-promoted (Z)-hydrochalcogenation of alkynes with DMSO/DMSO-d6 as hydrogen/deuterium sources, giving chalcogenated (Z)-olefins in good yields and with excellent regioselectivity. These reagents, easily synthesized from halostibines with in situ generated [Zn(ER)2] at room temperature within a few minutes, could be also used in the base-promoted C(sp3)-S(Se) cross-coupling with C(sp3)-X and copper-catalyzed C(sp2)-S(Se) cross-coupling with C(sp2)-X (X = F, CI, Br, I) under mild conditions. This protocol could also be simply extended to organobismuth complexes (Bi-ER) with good functional tolerance.

CF3SO2Na-Mediated Five-Component Carbonylation of Triarylboroxines with TMSCF3 and THF/LiOH/NaI to Give Aroyloxyalkyl Iodides.

Herein, we developed an efficient and transition-metal-free multicomponent coupling reaction for the synthesis of aroyloxyl alkyl iodides. In the reaction among 2,4,6-triarylboroxines, THF, TMSCF3, LiOH, and NaI, five-component reactions could be precisely controlled by modulating CF3SO2Na, supplying one type of aroyloxyl alkyl iodides in moderate to high yields. The reaction exhibits good functional group tolerance and a wide substrate scope and can be easily transformed into other useful compounds. The mechanism is proposed on the basis of the control experiments.

Copper-Catalyzed Regioselective Olefination and Trifluoromethylation of Carboxylic Acids To Give (Z)-Trifluoromethyl Enol Esters.

Herein, we describe a method to produce (Z)-trifluoromethyl enol esters via the olefination and trifluoromethylation of carboxylic acids with TMSCF3. This synthetic method uses inexpensive and easy-to-handle TMSCF3. It employs a commercially available CuCl catalyst to transform a broad range of carboxylic acids into versatile (Z)-trifluoromethyl enol esters with good regio- and stereoselectivity. This protocol allows the concise synthesis of highly functionalized (Z)-trifluoromethyl enol esters directly from carboxylic acids.

One-pot synthesis of phosphorylnaphth[2,1-d]oxazoles and products as P,N-ligands in C-N and C-C formation.

Phosphanylnaphtho[2,1-d]oxazoles were synthesized successfully through one-pot phosphonation of naphthoquinone with diaryl(alkyl)phosphine oxides and Cu-catalyzed oxidative condensation with imines, followed by methylation and reduction. Upon applying 4-phosphanylnaphtho[2,1-d]oxazole as a P,N-chelating ligand, Pd-catalyzed C-N formation of amines or nitrobenzene as well as Ni-catalyzed C-C formation and the synthesis of quinoline proceeded successfully. The reaction was facilely scaled up to give N-benzylaniline 15a in a gram scale synthesis. This research provided a facile and convenient protocol to synthesize phosphanylnaphtho[2,1-d]oxazoles, which could be applied as an efficient P,N-ligand in transition-metal-catalyzed C-N and C-C formation to produce the desired products in high yields with wide functional group tolerance under small catalyst loading, solvent-free conditions in many reactions.

Synthesis of (Deoxy)difluoromethylated Phosphines by Reaction of R2P(O)H with TMSCF3 and Their Application in Cu(I) Clusters in Sonogashira Coupling.

R2PCF2H ligands and their R2P(O)CF2H precursors were synthesized from R2P(O)H with TMSCF3 by simply modulating the H2O concentration via deoxydifluoromethylation and difluoromethylation. The air sensitive R2PCF2H phosphines can be stabilized in Cu(I) clusters as ligands. Within these Cu(I) clusters, the Sonogashira cross-coupling reaction can proceed fast and efficiently using terminal alkynes and aryl iodides within 15 min at room temperature under air to give a variety of diaryl(alkyl)acetylenes in good yields (49 examples, yields of ≤99%). Six of the internal alkynes present in drug precursors can be obtained using this protocol in good yields. The mechanism is proposed on the basis of control experiments.

FeO(OH)@C-Catalyzed Selective Hydrazine Substitution of p-Nitro-Aryl Fluorides and their Application for the Synthesis of Phthalazinones.

An efficient hydrazine substitution of p-nitro-aryl fluorides with hydrazine hydrates catalyzed by FeO(OH)@C nanoparticles is described. This hydrazine substitutions of p-nitro-aryl fluorides bearing electron-withdrawing groups proceeded efficiently with high yield and selectivity. Similarly, hydrogenations of p-nitro-aryl fluorides containing electron-donating groups also smoothly proceeded under mild conditions. Furthermore, with these prepared aryl hydrazines, some phthalazinones, interesting as potential structures for pharmaceuticals, have successfully been synthesized in high yields.

Cu(I)-Catalyzed C-H Alkenylation of Tertiary C(sp3)-H Bonds of 3-Aryl Benzofuran-2(3H)-ones to Give Z- and E-Styrene Containing Quaternary Carbon Centers with 99/1 Regioselectivity.

The synthesis of isomerically pure olefins containing all-carbon quaternary centers is a challenging issue. Herein, we developed an efficient protocol for the synthesis of (Z)-olefins (27 examples, yield up to 97%, Z/E up to 99/1) and (E)-olefins (16 examples, yield up to 94%, E/Z up to 99/1) containing all-carbon quaternary centers. This protocol is adopted for the copper-catalyzed regioselective C-H alkenylation of the tertiary C(sp3)-H bond of 3-aryl benzofuran-2(3H)-ones with alkyne and alkenes. A diverse range of functional groups in the substrates is well-tolerated, such as F, Cl, Br, Me, OMe, ester, CF3, etc. A gram scale experiment was performed in good yield, and the radical mechanisms are also proposed based on the control experiments.

Cu-Catalyzed Dual C-O Bonds Cleavage of Cyclic Ethers with Carboxylic Acids, NaI, and TMSCF3 to Give Iodoalkyl Ester.

Herein, by dual C-O bond cleavage of cyclic ethers with Cu catalysis, we eventually led to the development of a selective three-component coupling of commercially available chemicals, carboxylic acids, ethers, and halogens to synthesize more than 70 iodoalkyl esters in the presence of TMSCF3. This allows for the concise synthesis of highly functionalized iodoalkyl esters directly. And the synthetic insect pheromones were also disclosed.

Pd-Catalyzed Cross-Coupling of Sb-Aryl Stibines with Halogenomethyl Arenes to Give Unsymmetirc Diarylmethanes.

Herein, we describe a general method for the synthesis of unsymmetric diarylmethanes from (hetero)aryl methyl halides and Sb-aryl stibines. This protocol shows a broad substrate scope and a good functional group tolerance. Drug molecules, including beclobrate 3al and bifemelane 3as, and drug derivatives, including celecoxib 3p, ibuprofen 3ao, and probenecid 3ap, were efficiently synthesized on a gram scale. The possible mechanism is proposed on the basis of the results of control experiments.