Tandem vinylogous 1,2-addition/anionic oxy-Cope reaction leading from butadiene sulfone to an orthogonally functionalized bicycle.
Here we present a transition metal-free synthesis of a rigid, orthogonally functionalized bicyclic sulfone, starting from readily available reagents. The transformation proceeds via a tandem vinylogous 1,2-addition/anionic oxy-Cope sequence, followed by a second vinylogous ketone addition. Stereochemical assignments suggest that the anionic oxy-Cope reaction proceeds exclusively through a boat-shaped transition state. The product of the two-step sequence can be further functionalized through subsequent chemo- and diastereoselective transformations, suggesting possible applications in medicinal chemistry or materials chemistry.
Brant
Michael G
MG
Department of Chemistry, University of Victoria, Victoria, BC, Canada, V8W 3V6.
Bromba
Caleb M
CM
Wulff
Jeremy E
JE
D000838:Anions / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis* / Q000737:chemistry; D002070:Butadienes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism; D013450:Sulfones / Q000138:chemical synthesis* / Q000737:chemistry*
D000838:Anions; D019086:Bridged Bicyclo Compounds, Heterocyclic; D002070:Butadienes; D013450:Sulfones