110792-92-2

Upstream product

• 2579-22-8 Phenylpropargyl aldehyde 
• 13423-48-8 triphenylheptylphosphonium bromide 
• 125378-24-7 1-octenyl iodide 
• 536-74-3 phenylacetylene 
• 16664-50-9 1-phenyl-1-decyne 
• 58672-84-7 1-(deca-1,3-diynyl)benzene 
• 591-50-4 iodobenzene 
• 2807-10-5 (E)-dec-3-en-1-yne 
• 52356-93-1 (Z)-1-octenyl iodide 
• 61827-88-1 (Z)-dec-3-en-1-yne 
• 461463-75-2 (E)-1-phenyl-4-(tributylstannyl)dec-3-en-1-yne 
• 42599-17-7 (E)-1-iodo-1-octene 
• 629-05-0 n-octyne 
• 4440-01-1 lithium phenylacetylide 

Downstream Products

• 54985-33-0 cis-1-(n-Hexyl-1-hydroxy-4-phenyl)-3-buten 
• 54985-37-4 trans-1-(n-Hexyl-1-hydroxy-4-phenyl)-3-buten 

Relevant academic research and scientific papers

Oxovanadium(V)-induced oxidation of alkenylzirconocenes for facile inter- and intramolecular coupling

The oxidation reaction of (E)-1-alkenylchlorozirconocenes with an oxovanadium(V) compound at room temperature led to intermolecular homocoupling, giving the corresponding (E,E)-dienes stereoselectively. (E)-1-Alkenyl-1-alkynylzirconocenes underwent the oxovanadium(V)-induced intramolecular cross-coupling of organic substituents on zirconium, leading to the stereoselective formation of the (E)-enynes.

Copper-catalyzed synthesis of 1,3-enynes

We report a copper(I)-catalyzed procedure for the synthesis of 1,3-enynes. This method affords a variety of enynes in good to excellent yields. This method can tolerate a variety of functional groups, does not require the use of expensive additives, and is palladium-free.

From bis(silylene) and bis(germylene) pincer-type nickel(II) complexes to isolable intermediates of the nickel-catalyzed sonogashira cross-coupling reaction

The first [ECE]Ni(II) pincer complexes with E = SiII and E = GeII metallylene donor arms were synthesized via C-X (X = H, Br) oxidative addition, starting from the corresponding [EC(X)E] ligands. These novel complexes were fully characterized (NMR, MS, and XRD) and used as catalyst for Ni-catalyzed Sonogashira reactions. These catalysts allowed detailed information on the elementary steps of this catalytic reaction (transmetalation → oxidative addition → reductive elimination), resulting in the isolation and characterization of an unexpected intermediate in the transmetalation step. This complex, {[ECE]Ni acetylide → CuBr} contains both nickel and copper, with the copper bound to the alkyne π-system. Consistent with these unusual structural features, DFT calculations of the {[ECE]Ni acetylide → CuBr} intermediates revealed an unusual E-Cu-Ni three-center-two-electron bonding scheme. The results reveal a general reaction mechanism for the Ni-based Sonogashira coupling and broaden the application of metallylenes as strong σ-donor ligands for catalytic transformations.

Site-selective mono-titanation of conjugated diynes with a Ti(II) alkoxide reagent. Concise preparation of stereo-defined enynes and dienynes

Conjugated diynes underwent selective mono-titanation with a Ti(II) reagent to give 1:1 diyne - titanium alkoxide complexes, which reacted with proton, aldehyde, and another acetylene to give stereo-defined enynes, enynols, and dienynes.

Simple and efficient nickel-catalyzed cross-coupling reaction of alkenylalanes with alkynyl halides for synthesis of conjugated enynes

A NiCl2(PPh3)2/XantPhos catalyzed synthesis of conjugated enynes by the cross-coupling of terminal alkynyl halides with alkenylaluminum reagents at room temperature in DME solvent was developed under mild reaction conditions. The aryls bearing electron-donating or electron-withdrawing groups in alkynylhalides give the corresponding cross-coupling products conjugated enynes in good to excellent isolated yields up to 97%. This process was simple and easily performed, which provides an efficient method for the synthesis of conjugated enynes derivatives. On the basis of the experimental results, a possible catalytic cycle has been proposed.

Stereoselective Traceless Borylation–Allenation of Propargylic Epoxides: Dual Role of the Copper Catalyst

Chiral α-allenols are prepared with high diastereocontrol through an unprecedented and spontaneous β-oxygen elimination of an α-epoxy vinyl boronate. Stochiometric experiments and DFT calculations support a dual role of the copper catalyst, which orchestrates the hydroboration and the syn-elimination step.

Single electron transfer-induced coupling of alkynylzinc reagents with aryl and alkenyl iodides

Alkynylzinc reagents were found to undergo coupling with aryl and alkenyl iodides to give arylalkynes and alkenylalkynes without the aid of transition metals. The coupling reaction proceeds through a single electron transfer mechanism, where a substoichiometric amount of a phosphine works as an indispensable activator.

Arylsulfonylacetylenes as alkynylating reagents

The unexpected anti-Michael addition of RLi to β-substituted sulfonylacetylenes, followed by in situ elimination of the ion sulfinate, allows the alkynylation of C(sp2) and C(sp3). Aryl and heteroaryl acetylenes, enynes, and mono and dialkyl alkynes can be obtained in very high yields under very mild conditions, avoiding the use of transition metals as catalysts and, in many cases, haloderivatives as starting materials. Furthermore, the use of lithium 2-p-tolylsulfinyl benzylcarbanions as nucleophiles of these reactions allows their stereocontrolled alkynylation, affording enantiomerically pure alkynes or enantioenriched allenes depending on the protonating agent (NH4Cl or H2O).

Arylsulfonylacetylenes as alkynylating reagents of C sp 2 -H bonds activated with lithium bases

Chameleon: A new strategy for the synthesis of a wide variety of alkynyl derivatives by the reaction of substituted arylsulfonylacetylenes with organolithium species is described (see scheme). The high yields, the simplicity of the experimental procedure, the broad scope of this reaction, and the formation of Csp-C sp 2 bonds without using transition metals are the main features of this methodology. Copyright

Expanding the scope of arylsulfonylacetylenes as alkynylating reagents and mechanistic insights in the formation of Csp2-Csp and Csp 3-Csp bonds from organolithiums

We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an "anti-Michael" addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected "anti-Michael" reactions observed for substituted sulfonylacetylenes. A calculated conclusion: A new transition-metal-free strategy for the synthesis of any kind of alkynyl derivatives in high yields in the reaction of organolithium species with arylsulfonylacetylenes is presented (see scheme). Theoretical calculations provide a rational explanation and suggest that association of the organolithium to the electrophile is a previous step of their intramolecular attack and is responsible for the "anti-Michael" reaction. Copyright