474661-33-1

Upstream product

• 503-17-3 dimethylacetylene 
• 62063-67-6 bis(4-dimethylaminophenyl)ethyne 
• 698-70-4 4-Iodo-N,N-dimethylaniline 
• 74-99-7 prop-1-yne 
• 100-10-7 4-dimethylamino-benzaldehyde 
• 18708-16-2 p-(dimethylamino)benzaldehyde tosylhydrazone 
• 74-86-2 acetylene 
• 115784-58-2 N,N-dimethyl-4-(prop-2-yn-1-yl)aniline 
• 629-05-0 n-octyne 
• 7051-34-5 cyclopropylcarbinyl bromide 
• 74-83-9 methyl bromide 
• 17573-94-3 4-ethynyl-N,N-dimethylaniline 
• 590-93-2 2-Butynoic acid 
• 586-77-6 4-bromo-N,N-dimethylaniline 

Downstream Products

• 62063-67-6 bis(4-dimethylaminophenyl)ethyne 
• 503-17-3 dimethylacetylene 

Relevant academic research and scientific papers

Quantifying Error Correction through a Rule-Based Model of Strand Escape from an [ n]-Rung Ladder

The rational design of 3D structures (MOFs, COFs, etc.) is presently limited by our understanding of how the molecular constituents assemble. The common approach of using reversible interactions (covalent or noncovalent) becomes challenging, especially when the target is made from multivalent building blocks and/or under conditions of slow exchange, as kinetic traps and nonequilibrium product distributions are possible. Modeling the time course of the assembly process is difficult because the reaction networks include many possible pathways and intermediates. Here we show that rule-based kinetic simulations efficiently model dynamic reactions involving multivalent building blocks. We studied "strand escape from an [n]-rung ladder" as an example of a dynamic process characterized by a complex reaction network. The strand escape problem is important in that it predicts the time a dynamic system needs to backtrack from errors involving [n]-misconnections. We quantify the time needed for error correction as a function of the dissociation rate coefficient, strand valency, and seed species. We discuss the simulation results in relation to a simple probabilistic framework that captures the power law dependence on the strand's valency, and the inverse relationship to the rung-opening rate coefficient. The model also tests the synthetic utility of a one-rung (i.e., hairpin) seed species, which, at intermediate times, bifurcates to a long-lived, fully formed [n]-rung ladder and a pair of separated strands. Rule-based models thus give guidance to the planning of a dynamic covalent synthesis by predicting time to maximum yield of persistent intermediates for a particular set of rate coefficients and valency.

Trimethylsilyl-Protected Alkynes as Selective Cross-Coupling Partners in Titanium-Catalyzed [2+2+1] Pyrrole Synthesis

Trimethylsilyl (TMS)-protected alkynes served as selective alkyne cross-coupling partners in titanium-catalyzed [2+2+1] pyrrole synthesis. Reactions of TMS-protected alkynes with internal alkynes and azobenzene under the catalysis of titanium imido comple

Multicomponent Oxidative Trifluoromethylation of Alkynes with Photoredox Catalysis: Synthesis of α-Trifluoromethyl Ketones

The direct oxidative addition of CF3 and H2O to alkynes was achieved with photoredox catalysis to obtain α-trifluoromethyl ketones via rapid enol-keto tautomerization. The reaction exhibits high functional group tolerance and regioselectivity. Heterocycles of various sizes containing CF3 were synthesized from the α-CF3-substituted diketones obtained through the protocol, thereby demonstrating the versatile applicability of the method. Mechanistic studies of the reaction with isotopes provided insight into the reaction pathway.

Rhodium-Catalyzed Intermolecular Carbonylative [2 + 2 + 1] Cycloaddition of Alkynes Using Alcohol as the Carbon Monoxide Source for the Formation of Cyclopentenones

A highly regioselective rhodium-catalyzed intermolecular carbonylative [2 + 2 + 1] cycloaddition of alkynes using alcohol as a CO surrogate to access 4-methylene-2-cyclopenten-1-ones has been developed. In this transformation, the alcohol performs multiple roles, including generating the Rh-H intermediate, functioning as the CO source, and assisting in the isomerization of the alkyne. Alkynes can act as both the olefin and the alkyne partner in the cyclopentenone core.

Synthesis of terminal allenes through copper-mediated cross-coupling of ethyne with N-tosylhydrazones or α-diazoesters

Ethyne is employed as coupling partner in coppermediated cross-coupling reactions with N-tosylhydrazones and α-diazoacetate, leading to the development of a new synthetic method for terminal allenes. With this novel coupling method, the terminal allenes w

Organomagnesium-catalyzed isomerization of terminal alkynes to allenes and internal alkynes

Organomagnesium complexes 2 were synthesized from N,N-dialkylamineimine ligands 1 and dibenzylmagnesium by benzylation of the imine moiety. 3-Aryl-1-propynes reacted with 2 to form the corresponding tetraalkynyl complexes, which acted as catalysts for the transformation of these terminal alkynes into allenes and further to internal alkynes under mild conditions. To the best of our knowledge, this example is the first of an organomagnesium-catalyzed isomerization of alkynes. Notably, the reactions proceeded through temporally separated autotandem catalysis, thus allowing the isolation of the allene or internal alkyne species in good yields. Mechanistic experiments suggested that the catalytically active tetraalkynyl complexes consist of a tautomeric mixture of alkynyl-, allenyl-, and propargylmagnesium species.

Nickel-catalyzed sonogashira reactions of non-activated secondary alkyl bromides and iodides

A nicked reaction: The title reaction of terminal alkynes with non-activated secondary alkyl iodides and bromides was accomplished for the first time. This reaction provides a new and practical approach for the synthesis of substituted alkynes (see scheme; cod=cyclo-1,5-octadiene). Copyright

One-pot carboboration of alkynes using lithium borylcyanocuprate and the subsequent Suzuki-Miyaura cross-coupling of the resulting tetrasubstituted alkenylborane

We have developed a one-pot carboboration of internal alkynes using lithium borylcyanocuprates 3. Isolation of single crystals of 3·(thf) 3 enabled us to estimate its structural and spectroscopic features. Simple mixing of 3 with ester-substituted alkynes and alkynylarenes was followed by trapping of the resulting intermediate with electrophiles to give tetrasubstituted borylalkenes 4, 5, and 8 in moderate to good yields. Ligand exchange of 8ba from diamine to pinacol allowed us to explore further application of obtained pinacol ester 10ba to subsequent Suzuki-Miyaura cross-coupling reactions to give all-carbon substituted alkene 9ba. Copyright

Highly Active Trialkoxymolybdenum(VI) Alkylidyne Catalysts Synthesized by A Reductive Recycle Strategy

A systematic study of alkyne metathesis catalyzed by trialkoxymolybdenum(VI) alkylidyne complexes is reported, in which substrate functional groups, alkynyl substituents, and catalyst ligands are varied. Sterically hindered trisamidomolybdenum(VI) propylidyne complex 5 was prepared conveniently through a previously communicated reductive recycle strategy. Alcoholysis of 5 with various phenols/alcohols provides a set of active catalysts for alkyne metathesis at room temperature, among which the catalyst with p-nitrophenol as ligand shows the highest catalytic activity and is compatible with a variety of functional groups and solvents. A key finding that enabled the use of highly active molybdenum(VI) catalysts is replacement of the commonly used propynyl substituents on the starting alkyne substrates with butynyl groups. Under reduced pressure using 1,2,4-trichlorobenzene as an involatile solvent, the alkyne metathesis of butynyl substituted compounds proceeds well at 30 °C providing high yields (83%-97%) of dimers. Rationalization of the special role played by butynyl substrates is discussed.

(Z)-1-Aryl-1-haloalkenes as Intermediates in the Vilsmeier Haloformylation of Aryl Ketones

(Equation Presented) Vilsmeier reagents give (Z)-1-aryl-1-haloalkenes from aryl ketones bearing an electron-donating substituent at the ortho- or para-position. These haloalkenes are intermediates in the Vilsmeier haloformylation of the aryl ketones. Anot