Aluminum Hydroxide Secondary Building Units in a Metal–Organic Framework Support Earth-Abundant Metal Catalysts for Broad-Scope Organic Transformations
作者:Xuanyu Feng、Pengfei Ji、Zhe Li、Tasha Drake、Pau Oliveres、Emily Y. Chen、Yang Song、Cheng Wang、Wenbin Lin
DOI:10.1021/acscatal.9b00259
日期:2019.4.5
suggested σ-bond metathesis as a key step for the MIL-53(Al)-CoH-catalyzed addition reactions. MIL-53(Al)-FeCl competently catalyzed oxidative Csp3–H amination and Wacker-type alkene oxidation. XANES analysis revealed the oxidation of FeII to FeIII centers in the activated MIL-53(Al)-FeCl catalyst and suggested that oxidative Csp3–H amination occurs via the formation of FeIII–OtBu species by single electron
氧化铝(Al 2 O 3)表面的固有异质性对氧化铝负载的单中心非均相催化剂的开发提出了挑战,并阻碍了在分子水平上催化物种的表征以及对催化反应机理细节的阐明。 。这里,我们报告与式Al(μ在MIL-53(Al)的金属-有机骨架(MOF)的使用氢氧化铝次级结构单元的(事业部)2 -OH)(BDC)(BDC = 1,4-苯二甲酸)作为Al 2 O 3表面的均匀且在结构上定义的功能模拟物,用于负载地球富集金属(EAM)催化剂。该μ 2MIL-53(Al)SBU中的-OH基很容易去质子化,并用CoCl 2和FeCl 2金属化,从而得到MIL-53(Al)-CoCl和MIL-53(Al)-FeCl预催化剂,其特征在于粉末X射线衍射,氮吸附,元素分析,密度泛函理论和扩展X射线精细结构光谱学。用NaBEt 3 H活化将MIL-53(Al)-CoCl转化为MIL-53(Al)-CoH,可有效催化炔烃和腈的硼
Cobalt-Catalyzed Hydroarylations and Hydroaminations of Alkenes in Tunable Aryl Alkyl Ionic Liquids
Tunablearylalkylionicliquids (TAAILs) are a promising class of imidazolium- or triazolium-based ionicliquids. Contrary to “standard” all-alkyl ionicliquids, these carry an aryl ring together with a linear or branched alkyl chain. Their application in the cobalt-catalyzed hydroarylation/hydroamination of alkenes and anilines is presented. The catalytic system is tolerant toward air and is scalable
A convenient and practical copper-catalyzed reductive amination was discovered. In the presence of easily available and inexpensive Cu(OAc)2 various ketones react with anilines and molecular hydrogen to give the desired amines in high yields.
N-(p-Toluenesulfonyl)amino group can be directly introduced at allylic or benzylic carbon by treating alkenes or alkylarenes with t-butyl N-(p-toluenesulfonyl)peroxycarbamate in the presence of Cu(II) triflate.