Preparation and photochemical rearrangements of 2-phenyl-2,5-cyclohexadien-1-ones. an efficient route to highly substituted phenols.
[reaction: see text]. The synthesis of 2-phenyl-2,5-cyclohexadien-1-ones 1a-c and 2a-b from methyl 3-phenylbenzoate 4 and methyl 2-methoxy-5-phenylbenzoate 8 by the Birch reduction alkylation methodology is described. 1a-c and 2a-b undergo regiospecific photorearrangements at 300 nm to give tetrasubstituted phenols 14a-c and pentasubstituted phenols 18a-b, respectively. The type A photoproducts 17a-b resulting from irradiation of 2a-b at 366 nm have been isolated as approximately 1:1 diastereomer mixtures. When an optimized condition is applied, a single diastereomer of 17a is obtained.
Guo
Z
Z
Rensselaer Polytechnic Institute, Troy, New York 12180-3590, USA. guo@3dp.com
Schultz
A G
AG
Antoulinakis
E G
EG
D003512:Cyclohexanones / Q000138:chemical synthesis* / Q000737:chemistry*; D008027:Light; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D010100:Oxygen / Q000378:metabolism; D010636:Phenols / Q000138:chemical synthesis* / Q000737:chemistry*; D010777:Photochemistry; D013237:Stereoisomerism
D003512:Cyclohexanones; D010636:Phenols; D010100:Oxygen