A photochemical synthesis of functionalized trans-cyclooctenes driven by metal complexation.
Described is a scalable procedure for driving photochemical sytheses of trans-cyclooctene derivatives through metal complexation. During photoirradiation, reaction mixtures are continuously pumped through a column of a AgNO3-impregnated silica gel. The trans-cyclooctene derivative is selectively retained by the AgNO3-impregnated silica, but the cis-isomer elutes from the column back to the reaction flask, where it is photoisomerized and recirculated through the column. The method provides access to a range of usefully functionalized derivatives of trans-cyclooctene, including a derivative of 5-aza-trans-cyclooctene that underwent transannular cyclization upon treatment with bromine. The alkene stereochemistry is transferred with high fidelity to the hexahydropyrrolizine framework in the transannular cyclization.
Royzen
Maksim
M
Brown Laboratories, Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, USA.
Yap
Glenn P A
GP
Fox
Joseph M
JM
D018360:Crystallography, X-Ray; D003500:Cyclization; D034242:Cyclooctanes / Q000138:chemical synthesis* / Q000737:chemistry / Q000528:radiation effects*; D008958:Models, Molecular; D015394:Molecular Structure; D010777:Photochemistry; D012822:Silicon Dioxide / Q000737:chemistry*; D012835:Silver Nitrate / Q000737:chemistry*; D013237:Stereoisomerism; D014466:Ultraviolet Rays
D034242:Cyclooctanes; D012822:Silicon Dioxide; D012835:Silver Nitrate