182920-41-8Relevant academic research and scientific papers
A surprising switch from the Myers-Saito cyclization to a novel biradical cyclization in enyne-allenes: Formal diels-alder and ene reactions with high synthetic potential
Schmittel, Michael,Keller, Manfred,Kiau, Susanne,Strittmatter, Marc
, p. 807 - 816 (2007/10/03)
If there is an aryl substituent on the acetylene terminus of enyne allenes, then its reaction mode may be changed from the Myers-Saito cyclization to a novel C2-C6 cyclization resulting in a net intramolecular Diels-Alder or ene reaction. As a consequence, the thermal cyclization of readily accessible acyclic enyne allenes can be utilized for the synthesis of complex benzofulvene and benzofluorene derivatives. Kinetic results of the C2-C6 cyclization reaction indicate a two-step reaction pathway with a benzofulvene biradical intermediate.
Steric effects in enyne-allene thermolyses: Switch from the Myers-Saito reaction to the C2-C6-cyclization and DNA strand cleavage
Schmittel, Michael,Kiau, Susanne,Siebert, Torsten,Strittmatter, Marc
, p. 7691 - 7694 (2007/10/03)
The thermal reaction of enyne-allenes 1 with large substituents (tert.-butyl, trimethylsilyl) at the acetylene terminus leads to C2-C6 cyclization products presumably via an intermediate benzofulvene biradical, whereas with a hydrogen substituent the expected Myers-Saito cycloaromatization product is formed. Effective DNA strand scission can be observed when no intramolecular pathway is available.
Switching from the Myers Reaction to a New Thermal Cyclization Mode in Enyne-Allenes
Schmittel, Michael,Strittmatter, Marc,Kiau, Susanne
, p. 4975 - 4978 (2007/10/02)
Through variation of the substituents at the acetylene terminus in enyne-allenes the reaction mode may be changed from the Myers- to a novel C-2-C-6 cyclization reaction.This thermal cyclization of acyclic enyne-allenes in high yields allows the synthesis
