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This content will become publicly available on September 8, 2026

Title: Isocyanoalkenes: Occurrence, Syntheses, and Reactivity
Isocyanoalkenes are a largely underexplored subset of isocyanides whose natural occurrence, synthesis, and reactivity are elucidated in this review. The discussion begins with an overview of the biosynthesis and natural occurrence, which provides a valuable context for the synthetic approaches to these unusual π-substituted alkenes. Building on this foundation, the review explores the characteristic reactivity of isocyanoalkenes, which is shaped by the strong electron-withdrawing nature of the isocyanide group and an almost complete lack of π-conjugation. Two primary modes of reactivity are highlighted: conjugate additions – especially in systems containing additional electron-withdrawing substituents – and radical additions to the isocyanide, often followed by annulation via iminyl radical intermediates. Special attention is given to two particularly versatile isocyanoalkenes – β-dimethylaminoisocyanoacetates and β-bromoisocyanoacetates – which readily undergo nucleophilic addition–elimination–cyclization sequences to efficiently assemble nitrogen-containing heterocycles. Overall, this review underscores the synthetic potential of isocyanoalkenes and highlights their emerging value in the construction of diverse heterocyclic scaffolds.  more » « less
Award ID(s):
1953128
PAR ID:
10641500
Author(s) / Creator(s):
;
Publisher / Repository:
Synthesis
Date Published:
Journal Name:
Synthesis
ISSN:
0039-7881
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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