有机自由基通常是具有异常高反应性的短寿命中间体。从战略上讲,实现由有机自由基介导的合成有用的转化需要有效的引发和选择性终止事件。在这里,我们报告了一种新的催化策略,即双金属自由基氧化还原继电器,用于环氧化物向烯丙醇的区域和立体选择性重排。这种方法利用了 Ti 和 Co 配合物的丰富氧化还原化学,并将还原性环氧化物开环(引发)与氢原子转移(终止)相结合。至关重要的是,在影响关键的成键和断裂事件时,Ti 和 Co 催化剂彼此进行质子转移/电子转移以实现周转,从而构成真正协同的双催化系统。
Epoxydation aerobique des terpenes naturels: etude de l'activité catalytique des nouveaux complexes Ru-1,2,4-triazepines
作者:Naı̈ma Fdil、My Youssef Ait Itto、Mustapha Ait Ali、Abdellah Karim、Jean-Claude Daran
DOI:10.1016/s0040-4039(02)02072-5
日期:2002.11
Aerobic epoxidation of a range of natural terpenic olefines was carried out by using the triazepinic complexes [RuCl(TAZO)(p-cymene)](2) C-2 and [Ru(TAZS)(p-cymene)](2) C-2, recently prepared from [RuCl2(p-cymene)](2) and the corresponding 1,2,4-triazepines (HTAZO and H(2)TAZS). While, good similar stereoselectivity was observed for the two complexes, C-1, was shown to be more effective and chemioselective. (C) 2002 Elsevier Science Ltd. All rights reserved.
US8742145B2
申请人:——
公开号:US8742145B2
公开(公告)日:2014-06-03
Bimetallic Radical Redox-Relay Catalysis for the Isomerization of Epoxides to Allylic Alcohols
作者:Ke-Yin Ye、Terry MCallum、Song Lin
DOI:10.1021/jacs.9b04993
日期:2019.6.19
exceptionally high reactivity. Strategically, achieving synthetically useful transformations mediated by organic radicals requires both efficient initiation and selective termination events. Here, we report a new catalytic strategy, namely, bimetallic radical redox-relay, in the regio- and stereoselectiverearrangement of epoxides to allylic alcohols. This approach exploits the rich redox chemistry of Ti
有机自由基通常是具有异常高反应性的短寿命中间体。从战略上讲,实现由有机自由基介导的合成有用的转化需要有效的引发和选择性终止事件。在这里,我们报告了一种新的催化策略,即双金属自由基氧化还原继电器,用于环氧化物向烯丙醇的区域和立体选择性重排。这种方法利用了 Ti 和 Co 配合物的丰富氧化还原化学,并将还原性环氧化物开环(引发)与氢原子转移(终止)相结合。至关重要的是,在影响关键的成键和断裂事件时,Ti 和 Co 催化剂彼此进行质子转移/电子转移以实现周转,从而构成真正协同的双催化系统。
A recyclable hybrid manganese(III) porphyrin magnetic catalyst for selective olefin epoxidation using molecular oxygen
作者:Lucas D. Dias、Rui M. B. Carrilho、César A. Henriques、Giusi Piccirillo、Auguste Fernandes、Liane M. Rossi、M. Filipa Ribeiro、Mário J. F. Calvete、Mariette M. Pereira
DOI:10.1142/s108842461850027x
日期:2018.4
magnetic nanocomposite is described. Moreover, a sustainable methodology for epoxidation of olefins is reported, using O[Formula: see text] as a green oxidant and the magnetic nanoparticle as a recyclable catalyst. High activity in alkene oxidation was observed, with full selectivity for epoxide formation. The magnetic catalyst presented high stability, being recovered and reused in five consecutive runs