Synthesis of substituted benzenes and phenols by ring-closing olefin metathesis.
New synthetic approaches to substituted aromatic compounds are reported. Ring-closing olefin metathesis (RCM)/dehydration and RCM/tautomerization are the key processes in the synthesis of substituted benzenes 3 and phenols 6, respectively. Readily accessible 1,5,7-trien-4-ols 7, which are the precursors of benzenes, were prepared from beta-halo-alpha,beta-unsaturated aldehydes 11 or beta-halo-alpha,beta-unsaturated esters 19 by utilizing reliable transformations in which cross-coupling with vinylic metal reagents 12 and allylation with allylic metal reagents 13 were employed as carbon-carbon bond forming reactions. RCM of 7, followed by dehydration, afforded a wide variety of substituted benzenes 3. In addition, RCM of 1,5,7-trien-4-ones 9, which were prepared by oxidation of 7, furnished various substituted phenols 6 by automatic tautomerization.
Yoshida
Kazuhiro
K
Department of Chemistry, Graduate School of Science, Chiba University, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan. kyoshida@faculty.chiba-u.jp
Takahashi
Hidetoshi
H
Imamoto
Tsuneo
T
D000475:Alkenes / Q000737:chemistry*; D001555:Benzene Derivatives / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D003681:Dehydration; D015394:Molecular Structure; D010636:Phenols / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D000475:Alkenes; D001555:Benzene Derivatives; D010636:Phenols