Naphthalene Diels-Alder in a Self-Assembled Molecular Flask
Naphthalene Diels-Alder in a Self-Assembled Molecular Flask
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DOI：
10.1021/ja9107275
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发表时间：
2010-03-10
影响因子：
15
通讯作者：
Fujita, Makoto
中科院分区：
文献类型：
--
作者：
Murase, Takashi;Horiuchi, Shinnosuke;Fujita, Makoto
尽管它对周环反应的惰性在一般条件下，萘很容易发生Diels-Alder反应，当与合适的二亲试剂在自组装的宿主腔内共封装。反应物对的定位显著降低了反应的熵成本，并且在宿主腔内的预组织控制了反应的区域选择性和立体选择性：获得了电子不利的外加合物。我们的发现强调了这样一个事实，即在分子烧瓶中明智地调整底物的大小和形状，可以揭示出新的和不寻常的反应，否则不反应的分子。
Despite its inertness toward pericyclic reactions Under common conditions, naphthalenes readily undergo Diels-Alder reactions when coencapsulated with a suitable dienophile within the cavity of a self-assembled host. Localization of the reactant pair significantly reduces the entropic cost of the reaction, and preorganization within the host cavity controls both the regio- and stereoselectivity of the reaction: electronically disfavored exo adducts were obtained. and with substituted naphthalenes, the reaction takes place on the less electron-rich, unsubstituted ring Our findings highlight the fact that judicious tuning of substrate size and shape within molecular flasks can unveil new and unusual reactivities for otherwise unreactive molecules.