Copper-promoted and copper-catalyzed intermolecular alkene diamination.
Copper-promoted and copper-catalyzed intermolecular alkene diamination.
复制标题
DOI：
10.1002/anie.201003499
复制
发表时间：
2010-08-23
影响因子：
16.6
通讯作者：
Chemler, Sherry R.
中科院分区：
文献类型：
--
作者：
Sequeira, Fatima C.;Turnpenny, Benjamin W.;Chemler, Sherry R.
烯烃二胺化方法提供了在药物发现、材料和催化中有用的邻二胺最近报道了许多令人印象深刻的非对映选择性、对映选择性和催化烯烃二化方法。[2-7]分子内烯烃二聚形成氮杂环，主要是通过使用系链胺亲核试剂来完成的，其中两种胺的添加都以分子内方式发生（参见方案1）。通过使用钯、[4a]、镍[4b]和金[4c]催化剂和化学计量铜试剂[3]，这种烯烃二化策略已被简化为实践，并导致了许多有趣的化合物的合成，如双环磺胺、脲和胍。分子内/分子间的烯烃二化会导致一个新的氮杂环的聚合形成，同时安装一个不同功能化的胺取代基。在最近的一份报告中，Michael及其同事发现，使用钯催化剂与N-氟苯磺酰亚胺结合，可以形成具有- ch2 N (so2 Ph) 2取代的氮杂环在此，我们报道了一种新的铜（II）促进和催化的烯烃分子内/分子间二化反应，该反应涉及广泛的内部和外部胺源，形成不同功能化和各种氮杂环。重要的是，该通讯报告了第一个观察到基于催化剂的不对称诱导的分子内二化协议（见下文）。令人印象深刻的催化对映选择性分子间烯烃双聚已被报道，但没有对映选择性分子内变体已被报道在此报告我们在这一难以捉摸的转变方面的进展。
Olefin diamination methods provide powerful access to vicinal diamines useful in drug discovery, materials and catalysis.[1] A number of impressive diastereoselective, enantioselective and catalytic olefin diamination methods have been recently reported.[2–7]The intramolecular olefin diamination forms nitrogen heterocycles directly and has predominantly been accomplished by using tethered amine nucleophiles wherein both amine additions occur in intramolecular fashion (cf. Scheme 1). This olefin diamination strategy has been reduced to practice by using palladium,[4a] nickel [4b] and gold [4c] catalysts and stoichiometric copper reagents [3] and has resulted in the synthesis of a number of interesting compounds such as bicyclic sulfamides, ureas and guanidines. An intra/intermolecular alkene diamination would result in the convergent formation of one new nitrogen heterocycle along with the installation of a differently functionalized amine substituent. In a recent report, Michael and co-workers found that the use of a palladium catalyst, in combination with N-fluorobenzenesulfonimide led to the formation of nitrogen heterocycles with–CH 2 N (SO 2 Ph) 2 substitution.[5] Herein we report a new copper (II)-promoted and catalyzed intra/intermolecular diamination of alkenes that engages a wide range of internal and external amine sources for the formation of differently functionalized and various nitrogen heterocycles. Importantly, this communication reports the first intramolecular diamination protocol where catalyst-based asymmetric induction has been observed (vide infra). Impressive catalytic enantioselective intermolecular olefin diaminations have been reported,[2] but no enantioselective intramolecular variant has been reported.[8] Herein is reported our progress towards this elusive transformation.
登录
查看更多内容
影响因子：
5.2
作者：
Du H;Zhao B;Yuan W;Shi Y
通讯作者：
Shi Y
影响因子：
5.4
作者：
Sherman, Eric S.;Chemler, Sherry R.
通讯作者：
Chemler, Sherry R.
影响因子：
5.2
作者：
Fritz, Jonathan A.;Nakhla, Josephine S.;Wolfe, John P.
通讯作者：
Wolfe, John P.
影响因子：
5.2
作者：
Paderes MC;Chemler SR
通讯作者：
Chemler SR
影响因子：
3.2
作者：
Chemler SR
通讯作者：
Chemler SR