Cage expansion of alkyne clusters. An example of ligand assistance by alkyne substituents

Starting from dicobalt hexacarbonyl complexes of ene-ynes or hetero-ene-ynes, FeCo₂C₂-clusters can be prepared in high yield by metal fragment condensation with (biscyclooctene)(tricarbonyl)iron. The reaction takes place at temperatures below 0°C and allows the introduction of terminal alkynes into the cluster framework. It has been shown that the ease of these reactions is due to the free double bond in α-position of the coordinated triple bond, thus providing direct evidence for a ligand-assisted cage expansion reaction, unprecedented in this field of chemistry. The crystal structure of a FeCo₂C₂-cluster bearing a chiral Fe(CO)₃-diene substituent has been determined.     

Amido PNP complexes of iridium: Synthesis and catalytic olefin and alkyne hydrogenation

In situ lithiation of HN(o-C₆H₄PPh₂)₂ (H[ 1a ]) or HN(o-C₆H₄PiPr₂)₂ (H[ 1b ]) with nBuLi in THF at −35°C followed by addition of [Ir(μ-Cl)(COD)]₂ (COD = 1,5-cyclooctadiene) in toluene at −35°C generates 5-coordinate [ 1a ]Ir(η⁴-COD) ( 2a ) or 4-coordinate [ 1b ]Ir(η²-COD) ( 2b ), respectively. Oxidative addition of N-H in H[ 1b ] to [Ir(μ-Cl)(COD)]₂ affords square pyramidal [ 1b ]Ir(H)(Cl) ( 3b ). Metathetical reaction of 3b with LiBHEt₃ in the presence of 1 atm of H₂ in toluene produces [ 1b ]Ir(H)₂ ( 4b ). Both 2a and 4b are active for catalytic hydrogenation of olefins and alkynes under extremely mild conditions.     

The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies

The synthesis of a range of brominated-B_n-containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr₃ with appropriately substituted alkynes via a bromoboration/electrophilic C–H borylation sequence. The brominated-B_n-PAHs were isolated as either the borinic acids or B-mesityl-protected derivatives, with the latter having extremely deep LUMOs for the B₂-doped PAHs (with one example having a reduction potential of E_1/2 = −0.96 V versus Fc⁺/Fc, Fc = ferrocene). Mechanistic studies revealed the reaction sequence proceeds by initial alkyne 1,1-bromoboration. 1,1-Bromoboration also was applied to access a number of unprecedented 1-bromo-2,2-diaryl substituted vinylboronate esters directly from internal alkynes. Bromoboration/C–H borylation installs useful C–Br units onto the B_n-PAHs, which were utilised in Negishi coupling reactions, including for the installation of two triarylamine donor (D) groups onto a B₂-PAH. The resultant D–A–D molecule has a low optical gap with an absorption onset at 750 nm and emission centered at 810 nm in the solid state.

The synthesis of a range of brominated-B_n-containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr₃ with appropriately substituted alkynes via a bromoboration/electrophilic C–H borylation sequence.     

Coordinatively unsaturated alkyne complexes: synthesis of mono and bis-alkyne complexes of tungsten (II)

[WBr₂(CO₄]_n reacts with alkynes to give complexes [WBr₂CO(RCCR)₂]₂ (1) (R = R′ = Me, Et, Ph; R = Me, R′ = Ph), which react with nucleophiles L{L = CNBu^t, PPh₃, or P(OMe)₃} to give monoalkyne derivatives (WBr₂(CO)(RCCR′)L₂](2). An intermediate bis-alkyne adduct [WBr₂CO(MeCCMe)₂(CNBu^t)] (3) was isolated in the reaction of [WBr₂CO(MeCCMe)₂]₂ with CNBu^t illustrating that cleavage of the dimer (1) is the first stage in these reactions.     

Amine- and phosphine-free palladium(II)-catalyzed homocoupling reaction of terminal alkynes

An efficient, amine- and phosphine-free palladium(II)-catalyzed homocoupling of terminal alkynes has been developed. In the presence of PdCl₂, CuI, Me₃NO, and NaOAc, homocoupling of various terminal alkynes underwent smoothly to afford the corresponding diynes in moderate to high yields without any phosphine ligands. In contrast, the presence of a phosphine ligand (PPh₃) disfavored this palladium-catalyzed homocoupling procedure. Bases, solvents, and CuI have fundamental influence on the palladium-catalyzed homocoupling of terminal alkynes.     

Selective synthesis of α-methylenyl zirconacyclopentene via cross-coupling of alkyne and allene

α-Methylenyl zirconacyclopentenes are synthesized regio- and stereoselectively via reductive intermolecular cross-coupling of alkynes and allenes promoted by zirconocene species ‘Cp₂Zr’. An interesting reductive intramolecular coupling of the α-methylenyl zirconacyclopentene has been observed in the presence of DMAD/CuCl, resulting in the generation of cyclobutene with an exocyclic double bond. Polysubstituted 1,4-dienes can be given with high selectivity and good yields.     

A manganese(i)tricarbonyl-catalyst for near room temperature alkene and alkyne hydroarylation

Developing more efficient catalytic processes using abundant and low toxicity transition metals is key to enable their mainstream use in synthetic chemistry. We have rationally designed a new Mn(i)-catalyst for hydroarylation reactions that displays much improved catalytic activity over the commonly used MnBr(CO)₅. Our catalyst, MnBr(CO)₃(MeCN)₂, avoids the formation of the off-cycle manganacycle-(CO)₄ species responsible for low catalyst activity, allowing near room temperature hydroarylation of alkenes and alkynes with broad functional group tolerance including late stage functionalisation and diversification of bioactive molecules.

A Mn(i)-catalyst for hydroarylation reactions, MnBr(CO)₃(MeCN)₂, avoids the formation of the off-cycle manganacycle-(CO)₄ species responsible for low catalyst activity typical of MnBr(CO)₅, leading to mild and broad scope hydroarylation.     

Synthesis, characterization, and alkyne cyclotrimerization chemistry of titanium complexes supported by calixarene-derived bis(aryloxide) ligation

Proximally bridged calix[4]arene compounds (DESC)H₂ (3), (DMSHC)H₂ (4), (DMSMC)H₂ (5), and (DPSC)H₂ (6), in which one R₂Si group (R=alkyl or aryl) bridges adjacent oxygens, were synthesized via reaction between dialkyl- or diaryldichlorosilane and the corresponding calix[4]arene. Treatment of p-tert-butylcalix[4]arene with Ph₂SiCl₂ at room temperature or (o-MeC₆H₄)₂SiCl₂ at 80 °C gave (ClPh₂SiCl)₂Calix-H₂ (7) and (o-Tol₂SiCl)₂Calix-H₂ (8), respectively. Titanium dichloride complexes 9-12 (L₂TiCl₂, where L₂=DESC, DMSHC, DMSMC, or DPSC) were prepared in high yield from reaction of 3-6 with TiCl₄. The molecular structures of 7 and 12 were established by single-crystal X-ray diffraction studies. Reduction of 9, 11, and 12 with activated magnesium (Mg*) in the presence of an excess of Me₃SiCCH produced titananorbornadiene complexes L₂Ti{η⁶-1,2,4-C₆H₃(SiMe₃)₃} (13-15, L₂=DESC, DMSMC, or DPSC), which were characterized in solution. Catalytic cyclotrimerization of both terminal and internal alkynes was achieved using catalyst systems derived from L₂TiCl₂ complexes 9-12 and Mg*. For unsymmetrically substituted internal alkynes, preference for 1,2,4-substitution decreased as the size difference of the substituent groups decreased. The cyclotrimerization of PhCCMe was more facile when the calixarene-derived bis(aryloxide) ligand was DPSC versus DMSMC, suggesting that the DPSC ligand may provide a less crowded titanium center and exert greater kinetic control over the course of the cyclotrimerization.     

Hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide: selective synthesis of (Z)-1-alkenyl sulfides and selenides

A simple, stereoselective and efficient method for the hydrothiolation of terminal alkynes with diaryl disulfides and diphenyl diselenide has been developed. In the presence of CuI, rongalite, and Cs₂CO₃, a variety of disulfides underwent the reaction of terminal alkynes stereoselectively to afford the corresponding (Z)-1-alkenyl sulfides in moderate to excellent yields. It is noteworthy that hydroselenations of 1,2-diphenyldiselane with alkynes are also conducted smoothly to afford (Z)-1-alkenyl selenides in good yields under the standard conditions.     

Ready access to organoiodides: Practical hydroiodination and double-iodination of carbon-carbon unsaturated bonds with I2

By using I₂ or I₂/H₃PO₃ system, various alkenes and alkynes were converted to the corresponding alkyl and alkenyl iodides in good yields. In the presence of I₂, alkynes could be di-iodinated using H₂O as the solvent in air at room temperature. This method also features the simple work-up procedure since the pure product could be obtained by extraction. Additionally, for the first time, combining with the non-toxic and cheap phosphonic acid H₃PO₃, alkenes and alkynes were also hydroiodinated successfully, which provides a simple and practical approach for synthesis of organoiodides.     

Palladium-catalyzed cross-coupling of 2-haloselenophene with terminal alkynes in the absence of additive

We present herein our results of the Sonogashira coupling reaction of 2-haloselenophenes with terminal alkynes catalyzed by PdCl₂(PPh₃)₂, under co-catalyst free conditions and establish a new procedure to prepare (2-alkynyl)-selenophenes in good yields. The reaction proceeded cleanly under mild reaction conditions and was performed with propargylic alcohols, protected propargylic alcohols, propargylic amines, as well as alkyl, and aryl alkynes, in the presence of PdCl₂(PPh₃)₂, Et₃N, DMF, and in the absence of any supplementary additives. In addition, by this protocol (2,5-bis-alkynyl)-selenophenes were also obtained, in a one pot procedure, using 2,5-bis-iodoselenofene with an excess of terminal alkynes.     

SiO2-NHC-Cu(I): an efficient and reusable catalyst for [3+2] cycloaddition of organic azides and terminal alkynes under solvent-free reaction conditions at room temperature

A novel SiO₂-NHC-Cu(I) 3b was developed and used as a highly efficient catalyst for [3+2] cycloaddition of organic azides and terminal alkynes. In the presence of SiO₂-NHC-Cu(I) 3b (1 mol %), the reactions of terminal alkynes with organic azides underwent smoothly to generate the corresponding regiospecific 1,4-disubstituted 1,2,3-triazoles in excellent yields under solvent-free reaction conditions at room temperature. Furthermore, catalyst 3b was quantitatively recovered from the reaction mixture by a simple filtration and reused for 10 cycles without loss of its activity.     

Synthesis of trans‐Disubstituted Alkenes by Cobalt‐Catalyzed Reductive Coupling of Terminal Alkynes with Activated Alkenes

A cobalt‐catalyzed reductive coupling of terminal alkynes, RC?CH, with activated alkenes, R′CH?CH₂, in the presence of zinc and water to give functionalized trans‐disubstituted alkenes, RCH?CHCH₂CH₂R′, is described. A variety of aromatic terminal alkynes underwent reductive coupling with activated alkenes including enones, acrylates, acrylonitrile, and vinyl sulfones in the presence of a CoCl₂/P(OMe)₃/Zn catalyst system to afford 1,2‐trans‐disubstituted alkenes with high regio‐ and stereoselectivity. Similarly, aliphatic terminal alkynes also efficiently participated in the coupling reaction with acrylates, enones, and vinyl sulfone, in the presence of the CoCl₂/P(OPh)₃/Zn system providing a mixture of 1,2‐trans‐ and 1,1‐disubstituted functionalized terminal alkene products in high yields. The scope of the reaction was also extended by the coupling of 1,3‐enynes and acetylene gas with alkenes. Furthermore, a phosphine‐free cobalt‐catalyzed reductive coupling of terminal alkynes with enones, affording 1,2‐trans‐disubstituted alkenes as the major products in a high regioisomeric ratio, is demonstrated. In the reactions, less expensive and air‐stable cobalt complexes, a mild reducing agent (Zn) and a simple hydrogen source (water) were used. A possible reaction mechanism involving a cobaltacyclopentene as the key intermediate is proposed.     

Catalytic CN Bond Alkynylation of N‐Benzylic Sulfonamides with Terminal Alkynes

A new cross‐coupling reaction of N‐benzylic sulfonamides with terminal alkynes for the synthesis of internal alkynes is reported. In the presence of 5 mol% of (Tf)₂NH/Bi(OTf)₃ (1:1), a broad range of N‐benzylic sulfonamides react smoothly with arylacetylenes to afford structurally diverse internal alkynes in moderate to excellent yields. We reasoned that vinyl cations could be formed by the regioselective attack of terminal alkynes with benzyl cations generated in situ from N‐benzylic sulfonamides under acidic conditions, which then eliminated to form a carbon‐carbon triple bond.     

3‐(Diphenylphosphino)propanoic acid: an efficient ligand for the Pd/Cu‐catalyzed homo‐coupling of terminal alkynes in the presence of oxygen at room temperature

A simple, yet efficient system for PdCl₂/CuI to catalyze the homo‐coupling reactions of various terminal alkynes has been developed using 3‐(diphenylphosphino)propanoic acid as ligand in the presence of oxygen. The alkynes, including aromatic, heteroaromatic and aliphatic alkynes, were transformed at room temperature into the corresponding 1,3‐diynes in moderate to excellent yields. The turnover number was up to 1.04 × 10³. Copyright © 2015 John Wiley & Sons, Ltd.     

Encapsulation of N-heterocyclic carbene–gold (I) catalysts within magnetic core/shell silica gels: A reusable alkyne hydration catalyst

In this study, N-heterocyclic carbene–Au(I) complex, chloro[1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]gold (I), was successfully encapsulated within mesopores of a magnetic core/shell (γ-Fe₂O₃@SiO₂) silica gel through post-pore-size reduction by silylation reactions The post-reduction of the pore size not only minimizes the catalyst leaching during the alkyne hydration reactions but also eliminates any need for covalent modification of the catalyst or support surface. The resulting catalyst exhibits high activity in hydration reactions of various alkynes even under low catalytic loadings. The catalyst can be easily recycled from the reaction mixture using a magnet and can be reused in alkyne hydration reactions up to six times with only 52. wt% Au leaching.     

Facile synthesis and reactivity of CO-free monocyclopentadienylvanadium(I) alkyne complexes

Reactive CO-free monocyclopentadienylvanadium(I) complexes CpV(η²-RCCR′)(PMe₃)₂ (R,R′ = Ph,Ph; Ph,Me; Et,Et) can be synthesized by Mg reduction of CpVCl₂(PMe₃)₂ in the presence of free alkyne. Reaction with a second alkyne, or use of diynes in the reduction, produces metallacycles with the metallacyclopentatriene structure.     

Metal free synthesis of quinoxalines from alkynes via a cascade process using TsNBr2

A metal free protocol for the synthesis of quinoxalines from alkynes has been developed. The reaction was carried out by treating alkynes with TsNBr₂ in presence of O-phenylenediamines in a mixture of acetonitrile and water (9:1). This one-pot reaction proceeds via an oxidative transformation of alkynes to α,α-dibromoketones in presence of TsNBr₂ and eventually to quinoxalines in presence of 1,2-diamines in a cascade process.     

Synthesis of enol and vinyl esters catalyzed by an iridium complex

Enol and vinyl esters were successfully synthesized by the use of an iridium complex as a catalyst. The reaction of carboxylic acids with terminal alkynes in the presence of catalytic amounts of [Ir(cod)Cl]₂ and Na₂CO₃ gave the corresponding 1-alkenyl esters. The addition of carboxylic acids to alkynes principally took place in the Markovnikov fashion. In addition, by the use of an Ir complex combined with NaOAc various vinyl esters were prepared through the transvinylation between carboxylic acids and vinyl acetate.     

The conversion of alkynes into substituted cyclopropanes effected by CH2I2-R3Al (R = Me, Et, i-Bu)

The reaction of mono- and disubstituted alkynes with CH₂I₂-R₃Al (R = Me, Et, i-Bu) was studied. It was found that the reaction of alkynes with CH₂I₂ in the presence of Me₃Al gives β-iodoethyl-substituted cyclopropanes. The use of Et₃Al or i-Bu₃Al affords exclusively cyclopropylic organoaluminum compounds.