Stereoselective synthesis of spirocyclic ketones by Nazarov reaction.
[reaction: see text] The Suzuki-Miyaura cross-coupling reaction between alpha-ethoxydienyl boronates and lactone-derived vinyl triflates affords functionalized 6-(1-ethoxy-1,3-butadienyl)dihydropyran derivatives that undergo a Nazarov electrocyclic reaction under mild acidic conditions to give functionalized spirocyclic ketones. The product distribution and the stereoselectivity of the process are strongly dependent on the substitution of both the alpha-ethoxydiene and dihydropyran moieties. High stereoselectivity is observed in the presence of a C2-substituent on the dihydropyran moiety. The results are explained in terms of transition state geometries.
Prandi
Cristina
C
Dipartimento di Chimica Generale ed Organica Applicata, Università di Torino, C. so Massimo D'Azeglio, 48, I-10125 Torino, Italy. cristina.prandi@unito.it
Deagostino
Annamaria
A
Venturello
Paolo
P
Occhiato
Ernesto G
EG