Polyquinanes by [4 + 4] cycloaddition-transannular cyclization.
[reaction: see text] Photocycloaddition of 2-pyridones yields a rigid polycyclic product containing a 1,5-cyclooctadiene. The cis isomer, with the alkenes in close proximity, undergoes a transannular reaction when treated with chlorine to give a polyquinane product. The chlorination reaction involves migration of an amide nitrogen and forms a single isomer, generating eight stereogenic centers in two steps.
Ader
T A
TA
Department of Chemistry, State University of New York at Stony Brook, Stony Brook, New York 11794-3400.
Champey
C A
CA
Kuznetsova
L V
LV
Li
T
T
Lim
Y H
YH
Rucando
D
D
Sieburth
S M
SM
D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry*; D018360:Crystallography, X-Ray; D003500:Cyclization; D006571:Heterocyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008968:Molecular Conformation; D015394:Molecular Structure; D011728:Pyridones / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism; D013329:Structure-Activity Relationship
D000475:Alkenes; D006571:Heterocyclic Compounds; D007659:Ketones; D011728:Pyridones