6472-32-8Relevant academic research and scientific papers
Selective Alkynylallylation of the C?C σ Bond of Cyclopropenes
Chen, Ying-Chun,Jiang, Zeqi,Niu, Sheng-Li,Ouyang, Qin,Xiao, Qing,Zeng, Qiang
supporting information, p. 297 - 303 (2020/11/30)
A Pd-catalyzed regio- and stereoselective alkynylallylation of a specific C?C σ bond in cyclopropenes, using allyl propiolates as both allylation and alkynylation reagents, has been achieved for the first time. By merging selective C(sp2)-C(sp3) bond scission with conjunctive cross-couplings, this decarboxylative reorganization reaction features fascinating atom and step economy and provides an efficient approach to highly functionalized dienynes from readily available substrates. Without further optimization, gram-scale products can be easily obtained by such a simple, neutral, and low-cost catalytic system with high TONs. DFT calculations afford a rationale toward the formation of the products and indicate that the selective insertion of the double bond of cyclopropenes into the C-Pd bond of ambidentate Pd complex and the subsequent nonclassical β-C elimination promoted by 1,4-palladium migration are critical for the success of the reaction.
Small Rings, 33. Attempts to Synthesize Diphenyltetrahedrane
White, Emil H.,Winter, Rudolph E. K.,Graeve, Rolf,Zirngibl, Ulrich,Friend, Earl W.,et al.
, p. 3906 - 3915 (2007/10/02)
Carbene 7, formed on photochemical or thermal excitation of (2,3-diphenyl-2-cyclopropen-1-yl)diazomethane (6i), splits mostly into two acetylenes 8 and 9 instead of undergoing an intramolecular cycloaddition.Photolysis of the Masamune ketone 16 depending on the reaction conditions gives either p-terphenyl or a mixture of the two cyclooctatetraens 18 and 19.The intermediate formation of tetrahedrane 10 would fit into the mechanistic picture of this fragmentation.
