Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.
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Periselectivity in the Aza-Diels-Alder Reaction of 1-Azadienes with α-Oxoketenes: A Combined Experimental and Theoretical Study.
Molecules
October 2020
Aix Marseille Université, CNRS, Centrale Marseille, ISM2, 13397 Marseille, France.
Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.
View Article and Find Full Text PDFPeriselectivity in the aza-Diels-Alder Cycloaddition between α-Oxoketenes and -(5-Pyrazolyl)imines: A Combined Experimental and Theoretical Study.
J Org Chem
June 2020
Aix Marseille Univ, CNRS, Centrale Marseille, iSm2, Marseille, France.
The thermal 6π aza-Diels-Alder cycloadditions between α-oxoketenes, derived from a thermally induced Wolff rearrangement of 2-diazo-1,3-diketones, and -(5-pyrazolyl)imines as prototypical electron-rich 2-azadienes lead to two distinct sets of products, essentially as a function of the nature of the α-oxoketenes involved. For instance, cyclic five-membered α-oxoketenes lead preferentially to spiro hydropyridin-4-ones, which involves the α-oxoketenes as the 2π partners at their C═C double bond and the -(5-pyrazolyl)imines as the 4π partners at their 2-azadiene moiety. In contrast, other cyclic and acyclic α-oxoketenes lead preferentially to 1,3-oxazin-4-ones, which now involves the α-oxoketenes as the 4π partners at their 1-oxadiene moiety and the -(5-pyrazolyl)imines as the 2π partners at their C═N double bond.
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