Akther Thamina, Islam Md Monarul, Rahman Shofiur, Georghiou Paris E, Matsumoto Taisuke, Tanaka Junji, Redshaw Carl, Yamato Takehiko
Department of Applied Chemistry, Faculty of Science and Engineering, Saga University, Honjo-machi 1, Saga-shi, Saga 840-8502, Japan.
Org Biomol Chem. 2017 Apr 18;15(16):3519-3527. doi: 10.1039/c7ob00400a.
A series of syn- and anti-[2.n]metacyclophan-1-enes have been prepared in good yields by McMurry cyclizations of 1,n-bis(5-tert-butyl-3-formyl-2-methoxyphenyl)alkanes. Significantly, acid catalyzed rearrangements of [2.n]metacyclophan-1-enes afforded [n.1]metacyclophanes in good yield. The ratios of the products are strongly regulated by the number of methylene bridges present. The percentages of the rearrangement products increase with increasing length of the carbon bridges. Characterization and the conformational studies of these products are described. Single crystal X-ray analysis revealed the adoption of syn- and anti-conformations. DFT calculations were carried out to estimate the energy-minimized structures of the synthesized metacyclophanes.
通过1,n-双(5-叔丁基-3-甲酰基-2-甲氧基苯基)烷烃的麦克默里环化反应，以良好的产率制备了一系列顺式和反式-[2.n]间环芳-1-烯。值得注意的是，[2.n]间环芳-1-烯的酸催化重排以良好的产率得到了[n.1]间环芳。产物的比例受到存在的亚甲基桥数量的强烈调节。重排产物的百分比随着碳桥长度的增加而增加。描述了这些产物的表征和构象研究。单晶X射线分析揭示了顺式和反式构象的采用。进行了密度泛函理论计算以估计合成的间环芳的能量最小化结构。
