trans-2,2'-Bi(1-phenyladamantylidene): the most twisted biadamantylidene.
trans-2,2'-Bi(1-phenyladamantylidene): the most twisted biadamantylidene.
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trans-2,2-Bi(1-苯基亚金刚烷基)：最扭曲的亚金刚烷基。
DOI：
10.1021/jo020247
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发表时间：
2002
期刊：
影响因子：
--
通讯作者：
K. Takeuchi
中科院分区：
文献类型：
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作者：
T. Okazaki;Kohei Ogawa;T. Kitagawa;K. Takeuchi
2，2-二溴-1-苯基金刚烷经格氏偶联得到反式-2，2 '-二（1-苯基金刚烷亚基）（1-Ph）。单晶X-射线衍射分析表明，1-Ph具有23.2度的扭曲双键，比母体2，2 ′-二金刚烷亚基（1-H）和乙基取代衍生物（1-Et）的扭曲程度大得多。循环伏安图显示在0.87 V（相对于Fc/Fc（+））处的可逆电子氧化波，其比1-H低0.19 V，表明由于畸变导致HOMO能级显著增加。1-Ph与0.9equiv溴反应生成分子内Friedel-Crafts烷基化产物，而1-H和1-Me溴化分别生成桥连溴离子和重排产物2-（1-甲基-2-金刚烷亚基）-4-溴三环[5，3，1，0（3.9）]十一碳-4-烯。
The Grignard coupling of 2,2-dibromo-1-phenyladamantane gave trans-2,2'-bi(1-phenyladamantylidene) (1-Ph). Single-crystal X-ray analysis indicated that 1-Ph has a 23.2 degrees twisted double bond, which is much more distorted than that of parent 2,2'-biadamantylidene (1-H) and that of the ethyl-substituted derivative (1-Et). A cyclic voltammogram showed a reversible electron oxidation wave at 0.87 V vs Fc/Fc(+), which is 0.19 V lower than 1-H, indicating a significant increase in the HOMO energy level due to the distortion. The reaction of 1-Ph with 0.9 equiv of bromine gave an intramolecular Friedel-Crafts alkylation product, while bromination of 1-H and 1-Me has been reported to give a bridged bromonium ion and a rearranged product, 2-(1-methyl-2-adamantylidene)-4-bromotricyclo[5,3,1,0(3.9)]undec-4-ene, respectively.