1402160-72-8Relevant academic research and scientific papers
Synthesis of diverse benzotriazoles from aryne precursors bearing an azido group via inter- and intramolecular cycloadditions
Yoshida, Suguru,Morita, Takamoto,Hosoya, Takamitsu
, p. 726 - 728 (2016)
A diverse range of benzotriazoles were synthesized from various 3-(azidoalkoxy)aryne precursors, which were easily prepared by Mitsunobu etherification. Various bis-1,2,3-triazoles containing a benzotriazole skeleton were obtained via sequential azide-alkyne and azide-aryne cycloadditions. Intramolecular azido-aryne cycloaddition, conducted using the same starting materials, afforded new types of ring-fused benzotriazoles. In the latter case, the reaction proceeded efficiently even though the regioorientation of the azido group was the reverse of that usually observed in intermolecular reactions between 3-alkoxyarynes and an azide.
The Aryne-Abramov Reaction as a 1,2-Benzdiyne Platform for the Generation and Solvent-Dependent Trapping of 3-Phosphonyl Benzynes
Bembenek, Brianna M.,Foss, Samuel,Grieger, Abbigail M.,Harvat, Alisha N.,Haugen, Amber L.,Jiter, Naomi J.,Johnson, Andrew J.,Lilly, Julia A.,Lyle, Brandon J.,McNulty, Caitlin,Mraz, Gabriella L.,Petersen, Maya M. S.,Ripp, Ethan E.,Scanlon, Joseph D.,Schmid, Merranda L.,Stitgen, Abigail M.,Thein, Sierra A.,Willoughby, Patrick H.,Winchell, Shelby A.
, p. 10724 - 10746 (2021/07/28)
Synthetic methodology utilizing two aryne intermediates (i.e., a formal benzdiyne) enables the rapid generation of structurally complex molecules with diverse functionality. This report describes the sequential generation of two ortho-benzyne intermediates for the synthesis of 2,3-disubstituted aryl phosphonates. Aryl phosphonates have proven useful in medicinal chemistry and materials science, and the reported methodology provides a two-step route to functionally dense variants by way of 3-phosphonyl benzyne intermediates. The process begins with regioselective trapping of a 3-trifloxybenzyne intermediate by an O-silyl phosphite in an Abramov-like reaction to bond the strained Csp carbons with phosphorus and silicon. Standard aryne-generating conditions follow to convert the resulting 2-silylphenyl triflate into a 3-phosphonyl benzyne, which readily reacts with numerous aryne trapping reactants to form a variety of 2,3-difunctionalized aryl phosphonate products. DFT computational studies shed light on important mechanistic details and revealed that 3-phosphonyl benzynes are highly polarizable. Specifically, the distortion in the internal bond angles at each of the Csp atoms was strongly influenced by both the electronegativity of the phosphonate ester groups as well as the dielectric of the computational solvation model. These effects were verified experimentally as the regioselectivity of benzyl azide trapping increased with more electronegative esters and/or increasingly polar solvents. Conversely, replacing the conventional solvent, acetonitrile, with nonpolar alternatives provided attenuated or even inverted selectivities. Overall, these studies showcase new reactivity of benzyne intermediates and extend the aryne relay methodology to include organophosphonates. Furthermore, this work demonstrates that the regioselectivity of aryne trapping reactions could be tuned by simply changing the solvent.
Rhodium-catalyzed regioselective carboacylation of olefins: A C-C bond activation approach for accessing fused-ring systems
Xu, Tao,Dong, Guangbin
, p. 7567 - 7571 (2012/09/22)
Cut and sew: A rhodium-catalyzed regioselective carboacylation reaction of benzocyclobutenones was developed (see scheme). Directed by the pendant olefins, the C1-C2 bond is selectively cleaved rather than the C1-C8 bond. Subsequent alkene insertion leads to complex fused-ring systems. This reaction provides facile access to natural-product-like polycyclic structures in a chemoselective and atom-economic fashion. Copyright
