Department of Chemistry & Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, 08854, USA.
Chemistry. 2012 Oct 1;18(40):12864-72. doi: 10.1002/chem.201200602. Epub 2012 Aug 22.
The thermodynamically controlled reactions of water-soluble tetraformylcavitand 2 with two equivalents of H(2)N(CH(2))(n) NH(2) (n=2-4) in the presence of a suitable templating guest give hemicarceplexes 1 a-c⋅guest, the yield of which depends on the match between size and shape of the guest and that of the inner phase. These hemicarceplexes are dynamic and dissociate upon addition of acid and reform upon basification. In water, they exchange guests through temporary hydrolysis of imine bonds. To test 1 b as molecular reaction flask, 3-noradamantyldiazirine 6 was encapsulated and photolyzed at 350 nm to produce Bredt olefin protoadamantene 5 and 1-noradamantyldiazomethane 8 in a 4:1 ratio. Encapsulated protoadamantene is stable for days at room temperature in (CD(3))(2)SO/CD(3)CN (t(1/2) = 5.5 days) and has a lifetime of several minutes in D(2)O.
水溶性四醛杯[4]2 与两当量的 H(2)N(CH(2))(n)NH(2)（n=2-4）在合适模板客体存在下的热力学控制反应生成半冠醚配合物 1a-c⋅客体，其产率取决于客体与内相的大小和形状的匹配。这些半冠醚配合物是动态的，在加入酸时会解离，并在碱化时重新形成。在水中，它们通过亚胺键的临时水解交换客体。为了将 1b 用作分子反应瓶，将 3-降冰片基二氮杂环辛烷 6 封装并在 350nm 光解，以 4:1 的比例生成 Bredt 烯烃原金刚烷 5 和 1-降冰片基重氮甲烷 8。封装的原金刚烷在室温下（CD(3))(2)SO/CD(3)CN（t(1/2) = 5.5 天）中稳定数天，在 D(2)O 中的寿命为数分钟。
