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Trends in Organic Chemistry   Volumes    Volume 24 
Abstract
Discovery and disposition of the 1,4-diradical intermediate during reactions of isocyanates with alkenes
Dale F. Shellhamer, Marc C. Perry
Pages: 19 - 23
Number of pages: 5
Trends in Organic Chemistry
Volume 24 

Copyright © 2023 Research Trends. All rights reserved

ABSTRACT
 
Isocyanates react by a concerted mechanism for [2+2] cycloaddition reactions when the alkene is electron-deficient. Alkenes that are sufficiently electron-rich release a pi electron to the isocyanate which leads to a 1,4-diradical intermediate via the single electron transfer (SET) pathway. The triplet 1,4-diradical intermediate is in equilibrium with the singlet form. At temperatures around 15 oC and above the 1,4-diradical is in the triplet state; but it rearranges to the singlet form below 15 oC. The 1,4-diradical intermediate can close to give beta-lactam products, or it can be intercepted with a second isocyanate to give uracil products.
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