Calix[4]arenes with Two Different Chemical Modifications at the Bridges

• Published in: Journal of organic chemistry Vol. 76; no. 10; pp. 3664 - 3675
• Main Authors: Kuno, Lev, Biali, Silvio E
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 20.05.2011; Amer Chemical Soc
• Subjects: Alicyclic compounds; Alicyclic compounds, terpenoids, prostaglandins, steroids; Alkylating Agents - chemistry; Azides - chemistry; Calixarenes - chemistry; Carboxylic Acids - chemistry; Chemistry; Chemistry, Organic; Exact sciences and technology; General and physical chemistry; Halogenation; Molecular Conformation; Organic chemistry; Phenols - chemistry; Photochemistry; Physical chemistry of induced reactions (with radiations, particles and ultrasonics); Physical Sciences; Preparations and properties; Science & Technology; FUNCTIONALIZATION; REARRANGEMENT; CONFORMATIONAL BEHAVIOR; CALIXARENE; ACID; CALIX ARENES; P-BROMODIENONE ROUTE; METHYLENE BRIDGES; BOND; DERIVATIVES; Arene; Bromination; Calixarene; Photochemical reaction; Ketone; Macrocycle; Hydrolysis; Chemical modification; Aromatic compound; SN1 mechanism; Cyclophane; Inclusion compound; Chemical synthesis
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo200580m

Hexabromocalix[4]arene derivatives (3a and 3b) possessing pairs of dibromomethylene and bromomethylene groups located at distal or proximal positions of the calix scaffold were prepared via photochemical bromination of tetramethoxycalix[4]arene. The dibromomethylene groups undergo hydrolysis to afford calix[4]arenes possessing pairs of carbonyl groups and bromomethylene groups located at distal or proximal bridges (4a and 4b, respectively). The bromomethylene groups of 4 undergo reactions with nucleophiles under SN1 conditions to afford a wide array of derivatives possessing two different chemical modifications at the bridges.