title: An efficient Friedel-Crafts/oxa-Michael/aromatic annulation: rapid access to substituted naphtho[2,1-b]furan, naphtho[1,2-b]furan, and benzofuran derivatives.
abstract: Substituted naphthofurans and benzofurans are easily accessible by treatment of naphthols/substituted phenols with nitroallylic acetates through a substitution-elimination process promoted by cesium carbonate. Reactions between naphthols and aromatic/heteroaromatic-substituted nitroallylic acetates gave the desired functionalized naphthofurans in high to excellent chemical yields (14-97%). On the other hand, treatment of phenol derivatives (i.e., 3-dimethylamino-, 3-methoxy-, and 3,5-dimethoxyphenol) with various nitroallylic acetates afforded the corresponding benzofurans in moderate to good chemical yields (24-91%). The reaction proceeded through an interesting Friedel-Crafts S(N)2' process followed by intramolecular oxa-Michael cyclization and subsequent aromatization. A plot of log (k/kH) against Hammett constants σ(p) showed satisfactory linearity with a positive ρ value, indicating that the initial Friedel-Crafts-type S(N)2' process constituted the rate-determining step. This methodology has been applied to the synthesis of various novel C2 and C3 symmetric bis- and trisfurans by using catechol and phloroglucinol as the nucleophilic partners. The reactivity decreased when alkyl-substituted nitroallylic acetate systems were used. This might be related to the decreased electrophilic character of these substrates.
authors: Chemistry Department, National Taiwan Normal University, 88 Sec. 4, TingChow Rd., Taipei 116, Taiwan.
authors: Shaik
authors: S
authors: Anwar
authors: Wan-Yun
authors: WY
authors: Huang
authors: Chih-Hao
authors: CH
authors: Chen
authors: You-Song
authors: YS
authors: Cheng
authors: Kwunmin
authors: K
authors: Chen
mesh_terms: D001572:Benzofurans / Q000138:chemical synthesis* / Q000737:chemistry; D001688:Biological Products / Q000138:chemical synthesis* / Q000737:chemistry; D003500:Cyclization; D005663:Furans / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D001572:Benzofurans; D001688:Biological Products; D005663:Furans; D009281:Naphthalenes; C075195:naphtho(2,1-b)furan