通过光催化方法对芳香族底物进行脱芳烃化已经获得了越来越重要的关注,以达到分子复杂性。尽管人们将大量注意力放在非活性芳烃、萘酚和 N 基杂芳烃上,但迄今为止,芳胺仍处于背景中。在此,我们报道了一种在可见光照射下萘胺的有氧、脱氢羟基化的光催化策略。我们的研究强调了单线态氧的产生是芳香性破坏的可行机制,减轻了由目标芳胺直接氧化引起的选择性问题。最后,我们在后期多元化活动中展示了所获得的脱芳烃产品的合成价值。
CoPc/Cu(OAc)2-catalyzed N-arylation of amines with arylhydrazines leading to N-aryl amines
作者:Wang-Bin Sun、Pei-Zhi Zhang、Tao Jiang、Cheng-Kun Li、Li-Tao An、Adedamola Shoberu、Jian-Ping Zou
DOI:10.1016/j.tet.2016.08.058
日期:2016.10
The N-arylation of amines with arylhydrazines has been developed, achieving the selective cross-coupling of aryl radicals with amines to form N-aryl amines. The reaction uses air as an oxidant, CoPc and Cu(OAc)2 as catalysts. The reaction proceeds under mild conditions in air through a relay process, arylhydrazines are oxidized to aryldiazenes by CoPc, further oxidized to aryl radicals by air (O2)
Direct Intermolecular Aniline <i>Ortho-</i>Arylation via Benzyne Intermediates
作者:Thanh Truong、Olafs Daugulis
DOI:10.1021/ol302875x
日期:2012.12.7
A method for direct, transition-metal-free ortho-arylation of anilines by aryl chlorides, bromides, fluorides, and triflates has been developed. This methodology provides the most direct approach to 2-arylanilines since no protecting or directing groups on nitrogen are required. The arylation is functional-group tolerant, with alkene, ether, trifluoromethyl, dimethylamino, carbonyl, chloro, and cyano
已经开发了一种通过芳基氯化物、溴化物、氟化物和三氟甲磺酸酯对苯胺进行直接、不含过渡金属的邻位芳基化的方法。这种方法提供了最直接的 2-芳基苯胺方法,因为不需要氮上的保护或导向基团。芳基化是官能团耐受的,可以耐受烯烃、醚、三氟甲基、二甲氨基、羰基、氯和氰基官能团。对映体纯联萘二胺的苯基化提供具有>99% ee 的产物。
A compound represented by the following formula (1), wherein in the formula (1), A is a substituted or unsubstituted aromatic hydrocarbon ring group containing a nitrogen atom as a part of a substituent and having a fused ring composed of 5 or more rings, or a substituted or unsubstituted heterocyclic group containing a nitrogen atom as a part of the skeleton or a substituent and having a fused ring composed of 5 or more rings; B is a monovalent group represented by the following formula (b1); wherein in the formula (b1), *B is bonded with the nitrogen atom contained as a part of the skeleton of A or a substituent via a single bond.