铂催化水与氮杂苯并冰片烯加成开环反应研究

Study on platinum-catalyzed ring-opening reaction ofazabenzonorbornadienes with water

氧/氮杂苯并冰片烯的加成开环反应是构建C—C、C—杂原子键的高效方法,在过去的几十年里研究人员对此保持着广泛的兴趣,并发展了钌、钯、铱、铑、铂、铜、钴、镍等多种过渡金属催化剂.一些含有O、N、P、S等杂原子的亲核试剂也已被成功地用于氧、氮杂苯并冰片烯的开环反应.但水作为最简单的亲核试剂,其与氧、氮杂苯并冰片烯的加成开环反应目前仅能通过铑和铱催化剂实现.基于此,课题组首次开发了一种Pt(COD)Cl 2催化剂,高效地实现了水作为亲核试剂与氮杂苯并冰片烯的加成开环反应.该反应条件温和、收率较好、对映选择性优异(均高于95%),能高效制备一系列的高光学纯度二氢化萘衍生物.

The additional ring-opening reaction of azabenzonorbornadienes is an efficient method for constructing C-C and C-heteroatom bonds,and had attracted considerable interest in the past few decades by developing a variety of transition metal catalysts such as ruthenium,palladium,iridium,rhodium,platinum,copper,cobalt,nickel,etc.Some nucleophiles containing O,N,P,S have also been successfully applied.However,as the simplest nucleophile,the additional ring-opening reaction of water with azabenzonorbornadienes is currently developed only with iridium and rhodium catalysts.Therefore,our team developed a Pt(COD)Cl 2 catalyzed additional ring-opening reaction of azabenzonorbornadienes.The reaction conditions are mild,and is successfully applied to the efficient preparation of a series dihydronaphthalene of high optical purity in good yields with excellent enantioselectivities(>95%).