105456-83-5Relevant academic research and scientific papers
Synthesis of Cycloalkenones via the Intramolecular Cyclopropanation of Furanyl Diazo Ketones
Padwa, Albert,Wisnieff, Thomas J.,Walsh, Edward J.
, p. 5036 - 5038 (1986)
The reaction of α-diazo ketones derived from furanyl and benzofuranyl propionic acids with rhodium(II) acetate leads to cycloalkenones in high yield.Mechanistically,, the reaction involves addition of the keto carbene to the furanyl ?-bond followed by ele
Intramolecular Cyclopropanation Reaction of Furanyl Diazo Ketones
Padwa, Albert,Wisnieff, Thomas J.,Walsh, Edward J.
, p. 299 - 308 (2007/10/02)
α-Diazo ketones derived from furanyl- and benzofuranylpropionic acids were prepared, and their rhodium(II) acetate catalyzed behavior was studied.The results are consistent with a mechanism in which the key step involves addition of a keto carbenoid intermediate on to the furanyl ?-bond followed by an electrocyclic ring-opening reaction.In the case of the benzo-substituted furanyl system, the suspected bicyclic intermediate was isolated in high yield and its chemistry was subsequently investigated.The bicyclic ketone derived from 1-diazo-4-(2-benzofuryl)-2-butanone undergoes a novel thermal rearrangement to a benzopyranone derivative.This unexpected transformation can be rationalized in terms of a -cycloreversion reaction to give an ortho-quinoidal intermediate, which undergoes a subsequent electrocyclic ring closure followed by a 1,3-hydrogen shift.Furans with side chains of various lengths containing a diazomethyl keto group were also studied.The cyclization chemistry of the closely related diazothienylalkanone system was investigated and found to give products derived from an analogous intramolecular cyclopropanation reaction.
