1452773-86-2

Upstream product

• 18773-54-1 4-methyl-N,N-diprop-2-ynylbenzenesulfonamide 
• 536-74-3 phenylacetylene 
• 1228473-25-3 diethyl 1-(benzyloxycarbonylamino)-1-trifluoromethylbut-3-yne-1-ylphosphonate 
• 929616-31-9 methyl 2-[(benzyloxycarbonyl)amino]-2-(trifluoromethyl)pent-4-ynoate 
• 929616-33-1 methyl 2-[(tert-butoxycarbonyl)amino]-2-(trifluoromethyl)pent-4-ynoate 

Relevant academic research and scientific papers

Ruthenium-catalyzed cyclotrimerization of α-amino-α-propargyl carboxylates and phosphonates with 1,6-diynes: Synthesis of α-CF3-containing phenylalanine derivatives and their P-analogs

Ruthenium-catalyzed cocyclotrimerization of α-amino-α-propargyl-α-trifluoromethyl carboxylates and phosphonates with functional 1,6-diynes gives the corresponding CF3-containing phenylalanine derivatives and their phosphorus analogs.

Divergent Synthesis of Densely Substituted Arenes and Pyridines via Cyclotrimerization Reactions of Alkynyl Triazenes

Densely substituted fused aromatic triazenes can be prepared by [2 + 2 + 2] cyclotrimerization reactions of 1-alkynyl triazenes. The Cp*Ru-catalyzed cyclization proceeds well with both simple alkynyl triazenes and tethered 1-diynyl triazenes. Attractively, the methodology can be extended to pyridine synthesis by replacing an alkyne with a nitrile. The reaction is regioselective and yields the sterically more hindered product. The triazene group precisely installed on the synthesized aryl and pyridyl ring is a highly versatile moiety, which is effortlessly converted into the most important and frequently used functional aryl substituents, including fluorides. It is also suited for intramolecular transformations to afford a variety of valuable heterocycles. The coordination chemistry of alkynyl triazenes and Cp*RuCl was studied and led to the structural characterization of a Cp*RuCl(Η2-alkyne) complex, a Cp*RuCl(Η4-cyclobutadiene) complex, and an unusual dinuclear Ru complex with a bridging tetramethylfulvene ligand. Complexes of this type are potentially involved in catalyst deactivation pathways.

Cobalt Octacarbonyl-Catalyzed Scalable Alkyne Cyclotrimerization and Crossed [2 + 2 + 2]-Cycloaddition Reaction in a Plug Flow Reactor

Cobalt-catalyzed alkyne cyclotrimerization and crossed [2 + 2 + 2] cycloadditions are developed in a plug flow reactor. The protocol generally uses 5 mol % of Co2(CO)8 and is scalable at least at multigram scale. Efficient and scalable use of Co2(CO)8 for crossed reactions of diynes and alkynes has hardly any precedent.

Rhodium(I)-catalyzed [2+2+2+2] cycloaddition of diynes to form cyclooctatetraenes

Unique reactivity of a rhodium catalyst in the presence of many different Lewis basic additives was observed and studied. In the absence of additives, it was observed that a selective [2+2+2] reaction to form benzene products occurred; however, in the presence of an additive, optimally DMSO, the first rhodium(I)-catalyzed [2+2+2+2] reaction of alkynes occurred. A screen of different additives and catalysts was performed. Finally, a brief mechanistic study performed by using a ReactIR determined that DMSO coordinates to the catalyst, which affects the energetics of the reaction pathway. This appears primarily to raise the transition-state energy for the reductive elimination to form the benzene products. The first rhodium(I)-catalyzed [2+2+2+2] cycloaddition of alkynes is reported. The typical cyclotrimerization of alkynes to form benzene rings is still observed, but it was found to be significantly impacted by additives. A series of additives and mechanistic studies, performed using a ReactIR, were used to determine that DMSO is an efficient ligand for the RhI catalyst to impact the reaction mechanism. Copyright

Rhodium-catalyzed cyclization of diynes with nitrones: A formal [2+2+5] approach to bridged eight-membered heterocycles

N-aryl-substituted nitrones were employed as fiveatom coupling partners in the rhodium-catalyzed cyclization with diynes. In this reaction, the nitrone moiety served as a directing group for the catalytic C-H activation of the N-aryl ring. This formal [2+2+5] approach allows rapid access to bridged eight-membered heterocycles with broad substrate scope. The results of this study may provide new insight into the chemistry of nitrones and find applications in the synthesis of other heterocycles,.