Synthesis and Structures of [2.n]Metacyclophan-1-enes and their Conversion to Highly Strained [2.n]Metacyclophane-1-ynes

Thamina Akther, Md Monarul Islam, Zannatul Kowser, Taisuke Matsumoto, Junji Tanaka, Shofiur Rahman, Abdullah Alodhayb, Paris E. Georghiou, Carl Redshaw, Takehiko Yamato

Research output: Contribution to journalArticlepeer-review

Abstract

The syntheses of syn-[2.n]metacyclophan-1-enes (n = 5, 6, 8) in good yields using the McMurry cyclization of 1,n-bis(3-formyl-4-methoxyphenyl)alkanes are reported. Conversion of syn-[2.6]- and [2.8]metacyclophan-1-enes to the corresponding highly strained syn-type [2.6]- and [2.8]metacyclophane-1-ynes was achieved by successive bromination and dehydrobromination reactions. An attempted trapping reaction of the putative corresponding [2.5]metacyclophane-1-yne by Diels–Alder reaction with 1,3-diphenylisobenzofuran failed due to its smaller ring size and strained structure. X-ray crystallographic analyses show that the triple bonds in syn-[2.6]- and [2.8]metacyclophane-1-ynes are distorted from linearity with bond angles of 156.7° and 161.4°, respectively. A DFT (Density Functional Theory) computational study was conducted to determine the stabilities of different conformations of the target compounds.

Original languageEnglish
Pages (from-to)4167-4175
Number of pages9
JournalEuropean Journal of Organic Chemistry
Volume2020
Issue number27
DOIs
Publication statusPublished - Jul 23 2020

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry

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