Double Elimination Protocol for Synthesis of 5,6,11,12-Tetradehydrodibenzo[a,e]cyclooctene

✍ Scribed by Akihiro Orita; Daiki Hasegawa; Takehiko Nakano; Junzo Otera

• Publisher: John Wiley and Sons
• Year: 2002
• Tongue: English
• Weight: 123 KB
• Volume: 8
• Category: Article
• ISSN: 0947-6539
• DOI: 10.1002/1521-3765(20020503)8:9<2000::aid-chem2000>3.0.co;2-b

✦ Synopsis

A new method for constructing 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctene is described on the basis of one-pot double elimination protocol. The target molecule, which is the smallest cyclophane with alternate arylene-ethynylene linkage, is synthesized in 61 % yield through oxidative dimerization of ortho-(phenylsulfonylmethyl)benzaldehyde. The initial carbon-carbon bond formation between sp(3) carbons followed by stepwise conversion to sp(2) and finally sp carbons bypasses the difficulty encountered in direct coupling of the sp carbon in the terminal acetylene. The mechanism of this process is discussed. The Wittig-Horner-type coupling is a key reaction employed for the carbon-carbon bond formation. Generation of (E)-vinylsulfone moiety in the first coupling between alpha-sulfonyl anion and aldehyde functions is crucial for the effective second coupling to complete the cyclization. The syn-elimination of the (E)-vinylsulfone moieties in the cyclized intermediate furnishes the acetylenic bonds.