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Transannular Cyclizations of Medium‐Sized Cycloalkynes and Cycloalkynones Induced by Electro‐ and Photochemically Generated NO 3 Radicals
Author(s) -
Wille Uta,
Plath Christian
Publication year - 1996
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199719970117
Subject(s) - chemistry , radical , fragmentation (computing) , bicyclic molecule , photochemistry , reaction mechanism , scope (computer science) , medicinal chemistry , organic chemistry , catalysis , computer science , operating system , programming language
Transannular radical cyclizations of medium‐sized cycloalkynes and cycloalkynones induced by addition of NO 3 radicals to the C–C triple bond were studied. In the reaction of NO 3 with medium‐sized cycloalkynes oxidation of the triple bond to a carbonyl group occurred and formation of cis ‐fused bicyclic alkanones by transannular cyclization was observed. In the reaction of NO 3 radicals with medium‐sized cycloalkynones α,β‐epoxy ketones were formed in a transannular reaction sequence which can be formally considered as a retro Eschenmoser‐Ohloff fragmentation reaction. The scope and limitations of these reactions are presented and reaction mechanisms are proposed.