Dipole-Transmissive 1,3-Dipolar Cycloadditions for the Rapid Construction of Polycyclic N-Heterocycles: Synthetic and
Jackson S Henneveld1, Farshad Shiri2, Alireza Ariafard3
1Department of Chemistry, University of Otago, Dunedin, Otago, 9054, New Zealand.
Abstract:
The investigation of distinctive dipole-transmissive dipolar cycloaddition (DTDC) methodology and the formalisation of this concept is reported. A DTDC procedure was able to be developed by taking advantage of the structural complementarity of azide and diazoalkane 1,3-dipoles. Intramolecular azide-alkene 1,3-DCs followed by spontaneous dipole transmission upon work-up furnished intermediate α-diazoisoindole and α-diazoisoquinoline substrates bearing the key secondary diazoalkane 1,3-dipole. N-Derivatisation of the intermediate α-diazoisoindole and α-diazoisoquinolines with a tethered secondary dipolarophile followed by a subsequent 1,3-DC allowed for rapid construction of a range of functionalised polycyclic N-heterocycles. Integrated experimental and theoretical studies established requirements for product formation and revealed the likely mechanistic basis of divergent reactivity observed.
Related Concept Videos
Cycloaddition Reactions: Overview
Cycloaddition Reactions: MO Requirements for Thermal Activation
[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
Aromatic Hydrocarbon Cations: Structural Overview
Removing one hydrogen from the intervening CH2 group...
Cycloaddition Reactions: MO Requirements for Photochemical Activation
Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation


![Solid-phase Synthesis of [4.4] Spirocyclic Oximes](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F58508.jpg&w=3840&q=50)