4250-82-2

Usage

InChI:InChI=1/C12H14/c1-12(2,3)10-9-11-7-5-4-6-8-11/h4-8H,1-3H3

Upstream product

• 6738-06-3 phenylethynylmagnesium bromide 
• 507-19-7 t-butyl bromide 
• 591-50-4 iodobenzene 
• 917-92-0 3,3-Dimethylbut-1-yne 
• 960-71-4 triphenylborane 
• 61423-02-7 ethyl 1,1-dimethyl-3-phenylpropargyl acetate 
• 28995-94-0 1-Phenyl-2-tert-butansulfonyl-acetylen 
• 536-74-3 phenylacetylene 
• 40920-09-0 tert-butyl phenyl thioketone 
• 18107-18-1 diazomethyl-trimethyl-silane 
• 622-76-4 1-phenyl-1-butyne 
• 932-88-7 1-iodo-2-phenylethyne 
• 7436-90-0 2,2-dibromostyrene 
• 38442-51-2 tert-butylmercury chloride 

Downstream Products

• 35323-93-4 C₂₁H₂₄ 
• 23586-64-3 (3,3-dimethylbut-1-ene-1,1-diyl)dibenzene 
• 38690-88-9 (E)-(1-Chloro-3,3-dimethyl-1-butenyl)benzene 
• 17314-92-0 (3,3-dimethylbutyl)benzene 
• 56813-83-3 (E)-(1-Bromo-3,3-dimethyl-1-butenyl)benzene 
• 339546-51-9 1-Phenyl-1,2-dichlor-3,3-dimethyl-1-buten 
• 58696-49-4 ((Z)-1,2-Dichloro-3,3-dimethyl-but-1-enyl)-benzene 
• 58696-48-3 1-Phenyl-1,2-dichlor-3,3-dimethyl-1-buten 
• 58696-52-9 1-Phenyl-1-chlor-2-iod-3,3-dimethyl-1-buten 
• 69298-53-9 ((Z)-1,2-Dibromo-3,3-dimethyl-but-1-enyl)-benzene 
• 23764-10-5 cis,cis-1,4-Di-tert.-butyl-2,3-diphenyl-butadien-(1,3) 
• 35323-92-3 C₃₆H₄₄ 
• 23586-62-1 (Z)-1-deuterio-3,3-dimethyl-1-phenyl-1-butene 
• 61124-54-7 (Z)-3,3-Dimethyl-1-fluor-2-iod-1-phenyl-1-buten 

Relevant academic research and scientific papers

Inhibition of Reductive Elimination of Diorganopalladium Species by Formation of Tetraorganopalladates

Reductive elimination of (tBuCC)2Pd(PPh3)2 to give tBuCCCCBut (4) is strongly inhibited by an excess of LiCCBut through the formation of Li2Pd(CCBut)4, which does not readily decompose to produce (4); these results provide, for the first time, a mechanistic interpretation of the hitherto puzzling inhibitory action of highly electropositive metals, such as Li, in Pd-promoted coupling reactions.

Nickel-Catalyzed Sonogashira Coupling Reactions of Nonactivated Alkyl Chlorides under Mild Conditions

The two nickel chlorides1and2with [P,S] and [P,Se] bidentate ligands, respectively, were synthesized and used as catalysts for Sonogashira coupling reaction. Both1and2are efficient catalysts for Sonogashira C(sp3)-C(sp) coupling reactions. Comp

Direct Photoexcitation of Ethynylbenziodoxolones: An Alternative to Photocatalysis for Alkynylation Reactions**

Ethynylbenziodoxolones (EBXs) are commonly used as radical traps in photocatalytic alkynylations. Herein, we report that aryl-substituted EBX reagents can be directly activated by visible light irradiation. They act as both oxidants and radical traps, alleviating the need for a photocatalyst in several reported EBX-mediated processes, including decarboxylative and deboronative alkynylations, the oxyalkynylation of enamides and the C?H alkynylation of THF. Furthermore, the method could be applied to the synthesis of alkynylated quaternary centers from tertiary alcohols via stable oxalate salts and from tertiary amines via aryl imines. A photocatalytic process using 4CzIPN as an organic dye was also developed for the deoxyalkynylation of oxalates.

An Amine-Assisted Ionic Monohydride Mechanism Enables Selective Alkyne cis-Semihydrogenation with Ethanol: From Elementary Steps to Catalysis

The selective synthesis of Z-alkenes in alkyne semihydrogenation relies on the reactivity difference of the catalysts toward the starting materials and the products. Here we report Z-selective semihydrogenation of alkynes with ethanol via a coordination-induced ionic monohydride mechanism. The EtOH-coordination-driven Cl- dissociation in a pincer Ir(III) hydridochloride complex (NCP)IrHCl (1) forms a cationic monohydride, [(NCP)IrH(EtOH)]+Cl-, that reacts selectively with alkynes over the corresponding Z-alkenes, thereby overcoming competing thermodynamically dominant alkene Z-E isomerization and overreduction. The challenge for establishing a catalytic cycle, however, lies in the alcoholysis step; the reaction of the alkyne insertion product (NCP)IrCl(vinyl) with EtOH does occur, but very slowly. Surprisingly, the alcoholysis does not proceed via direct protonolysis of the Ir-C(vinyl) bond. Instead, mechanistic data are consistent with an anion-involved alcoholysis pathway involving ionization of (NCP)IrCl(vinyl) via EtOH-for-Cl substitution and reversible protonation of Cl- ion with an Ir(III)-bound EtOH, followed by β-H elimination of the ethoxy ligand and C(vinyl)-H reductive elimination. The use of an amine is key to the monohydride mechanism by promoting the alcoholysis. The 1-amine-EtOH catalytic system exhibits an unprecedented level of substrate scope, generality, and compatibility, as demonstrated by Z-selective reduction of all alkyne classes, including challenging enynes and complex polyfunctionalized molecules. Comparison with a cationic monohydride complex bearing a noncoordinating BArF- ion elucidates the beneficial role of the Cl- ion in controlling the stereoselectivity, and comparison between 1-amine-EtOH and 1-NaOtBu-EtOH underscores the fact that this base variable, albeit in catalytic amounts, leads to different mechanisms and consequently different stereoselectivity.

Practical synthesis of α,β-Alkynyl ketones by oxidative alkynylation of aldehydes with hypervalent alkynyliodine reagents

A practical, metal-free carbonyl C(sp2)H oxidative alkynylation of aldehydes with hypervalent alkynyliodine reagents without the use of any catalysts is described for the synthesis of various α,β-alkynyl ketones. Here, two different methods have been developed where limiting reagents or substrates can be switched, and adopted according to the valuableness of aldehyde substrates or hypervalent alkynyliodine reagents. These reactions proceed with a broad substrate scope and high functional-group compatibility.

Phosphorus(III)-Mediated, Tandem Deoxygenative Geminal Chlorofluorination of 1,2-Diketones

Tetrasubstituted carbon containing two different halogen substituents was constructed in a single-step operation by utilizing the carbene-like reactivity of dioxaphospholene through the tandem reaction of electrophilic and nucleophilic halogenating reagents. It was crucial to devise non-dealkylatable phosphoramidite, which enabled the efficient formation of geminal chlorofluorides from various 1,2-diketones with (PhSO2)2NF and n-Bu4NCl. In addition, selective functionalization of the chlorine substituent was demonstrated, and the absence of halogen scrambling was confirmed.

Nickel-Catalyzed Allylmethylation of Alkynes with Allylic Alcohols and AlMe3: Facile Access to Skipped Dienes and Trienes

We present herein an unprecedented allylative dicarbofunctionalization of alkynes with allylic alcohols. This simple catalytic procedure utilizes commercially available Ni(COD)2, triphenylphosphine, and inexpensive reagents, and delivers valuable skipped dienes and trienes with an all-carbon tetrasubstituted alkene unit in a highly stereoselective fashion. Preliminary mechanistic studies support the reaction pathway of allylnickelation followed by transmetalation in this dicarbofunctionalization of alkynes.

The Direct Conversion of α-Hydroxyketones to Alkynes

Alkynes are highly important functional groups in organic chemistry, both as part of target structures and as versatile synthetic intermediates. In this study, a protocol for the direct conversion of α-hydroxyketones to alkynes is reported. In combination with the variety of synthetic methods that generate the required starting materials by forming the central C-C bond, it enables a highly versatile fragment coupling approach toward alkynes. A broad scope for this novel transformation is shown alongside mechanistic insights. Furthermore, the utility of our protocol is demonstrated through its application in concert with varied α-hydroxyketone syntheses, giving access to a broad spectrum of alkynes.

Visible light promoted coupling of alkynyl bromides and Hantzsch esters for the synthesis of internal alkynes

A metal-free visible light promoted C(sp3)-C(sp) coupling reaction of alkynyl bromides and Hantzsch esters was developed, giving internal alkynes with primary, secondary, tertiary alkyl or other functional groups in good to high yields.

1-Aryltriazenes in the Suzuki, Heck, and Sonogashira Reactions in Imidazolium-ILs, with [BMIM(SO3H)][OTf] or Sc(OTf)3 as Promoter, and Pd(OAc)2 or NiCl2·glyme as Catalyst

1-Aryltriazenes, the protected and more stable form of aryl-diazonium species, can be conveniently unmasked with Br?nsted acidic-IL or Sc(OTf)3 and coupled with a host of aryl/heteroaryl boronic acids, styrenes, and aryl/alkyl acetylenes in the Suzuki, Heck and Sonogashira reactions in one-pot and in respectable isolated yields, by using palladium or nickel catalyst in readily available imidazolium ILs as solvent, under mild conditions. The scope of these reactions are explored, and the potential for recovery/reuse of the IL solvent is also addressed.