56598-71-1

Upstream product

• 591-50-4 iodobenzene 
• 1330631-43-0 (2-(2-(phenylethynyl)cyclohex-1-en-1-yl)vinyl)benzene 
• 67-56-1 methanol 
• 31144-31-7 (cyclohexene-1,2-diyl-bisethynyl)-bisbenzene 
• 871-84-1 1,7-Octadiyne 
• 501-65-5 diphenyl acetylene 

Relevant academic research and scientific papers

Unlocking the 5-exo Pathway with the AuI-Catalyzed Alkoxycyclization of 1,3-Dien-5-ynes

The first general regio- and stereoselective 5-exo gold(I)-catalyzed alkoxycyclization of a specific class of 1,5-enynes such as 1,3-dien-5-ynes has been described, despite 1,5-enynes being known to almost invariably proceed via endo cyclizations under gold-catalysis. The configuration of the terminal alkene in the starting 1,3-dien-5-yne plays a crucial role on the regiochemical outcome of the reaction. A wide variety of interesting alkoxy-functionalized alkylidenecyclopentenes have been synthesized from 1-monosubstituted (E)-1,3-dien-5-ynes. On the contrary, the corresponding Z isomers evolve affording formal 6-endo cyclization products. In addition, mechanistic exploration supports a highly stabilized carbocation as a key intermediate instead of a highly constrained cyclopropyl gold carbene from E isomers, and also accounts for the well differentiated reactivity observed between both E/Z geometrical isomers as well as for the stereochemical outcome of the reaction.

Ti(OiPr)4/nBuLi: An attractive reagent system for [2+2+2] cyclotrimerisation reactions

A convenient method for the [2+2+2] cyclotrimerisation of alkynes using Ti(OiPr)4/nBuLi is presented. Homotrimerisation of arylacetylenes proceeds within minutes with excellent regioselectivity. Moreover, the intermolecular construction of ABB heterotrimers can be achieved selectively from two different alkynes with similar electronic properties. The method is also suitable for the synthesis of pyridines.

Gold(I)-catalyzed tandem cyclization-selective migration reaction of 1,3-dien-5-ynes: Regioselective synthesis of highly substituted benzenes

Highly substituted benzene derivatives have been easily prepared in a regioselective way from readily available 1,3-hexadien-5-ynes through a gold(I)-catalyzed tandem reaction. The process involves an initial cyclization followed by a selective Wagner-Meerwein shift in which the migration preference seems to be determined by the ability to stabilize a positive charge.

Synthesis and protein degradation capacity of photoactivated enediynes

The viability of proteins as targets of thermally and photoactivated enediynes has been confirmed at the molecular level. Model studies using a labeled substrate confirmed the efficacy of atom transfer from diyl radicals produced from enediynes to form captodatively stabilized carbon centered aminoacyl radicals, which then undergo either fragmentation or dimerization. To exploit this finding, a family of enediynes was developed using an intramolecular coupling strategy. Derivatives were prepared and used to target specific proteins, showing good correlation between affinity and photoinduced protein degrading activity. The findings have potential applications in the design of artificial chemical proteases and add to our understanding of the mechanism of action of the clinically important enediyne antitumor antibiotics.

Synthesis of fused arylboronic esters via cobalt(0)-mediated cycloaddition of alkynylboronates with α,ω-diynes

(Chemical Equation Presented) Co2(CO)6-complexed alkynyl pinacolborane derivatives are readily transformed with functional group tolerance into fused arylboronates via the [2 + 2 + 2]cycloaddition to α,ω-diynes.

Polar Effects in the Transition State of the Bergman Cyclization

From the kinetic data of enediynes 1a-c it is concluded that electron withdrawing substituents are lowering the free activation energy in the Bergman cycloaromatization by decreasing the repulsion of the in-plane ?-orbitals.