Anti-Markovnikov Hydroamination of Racemic Allylic Alcohols to Access Chiral γ-Amino Alcohols

A ruthenium-catalyzed formal anti-Markovnikov hydroamination of allylic alcohols for the synthesis of chiral γ-amino alcohols is presented. Proceeding via an asymmetric hydrogen-borrowing process, the catalysis allows racemic secondary allylic alcohols to react with various amines, affording enantiomerically enriched chiral γ-amino alcohols with broad substrate scope and excellent enantioselectivities (68 examples, up to >99 % ee).     

~1H MAS NMR characterization of hydrogen over silica-supported rhodium catalyst

Hydrogen species in both SiO2 and Rh/SiO2 catalysts pretreated in different atmospheres (H2, O2, helium or air) at different temperatures (773 or 973 K) were investigated by means of 1H MAS NMR. In SiO2 and O2-pretreated catalysts, a series of downfield signals at -7.0, 3.8-4.0, 2.0 and 1.5-1.0 were detected. The first two signals can be attributed to strongly adsorbed and physisorbed water and the others to terminal silanol (SiOH) and SiOH under the screening of oxygen vacancies in SiO2 lattice, respectively. Besides the above signals, both upfield signal at -110 and downfield signals at 3.0 and 0.0 were also detected in H2-pretreated catalyst, respectively. The upfield signal at -110 originated from the dissociative adsorption of H2 over rhodium and was found to consist of both the contributions of reversible and irreversible hydrogen. There also probably existed another dissociatively adsorbed hydrogen over rhodium, which was known to be p hydrogen and in a unique form of "delocalized hydrogen". It wa     

负载型双噁唑啉催化剂上的不对称Diels-Alder反应

 分别以乙烷桥键磺酸官能化的有机-无机杂化介孔材料、十二钨磷酸铯、活化硅胶以及SBA-15为载体,通过非共价键作用制备了负载型双噁唑啉催化剂,并将该催化剂用于催化3-((E)-2-丁烯酰基)-1,3-噁唑啉-2-酮和环戊二烯的不对称Diels-Alder反应. 研究表明,催化剂的性能取决于载体本身以及载体表面阴离子的性质. 以SBA-15为载体时产物的对映体选择性较低,可归因于载体表面较低的羟基浓度.     

Mild and Convenient Synthesis of 1,2‐Dihydroquinolines from Anilines and Acetone Catalyzed by Ytterbium(III) Triflate in Ionic Liquids

A mild, convenient, and efficient process has been developed for the synthesis of 2,2,4‐trimethyl‐1,2‐dihydroquinolines by the reaction of anilines with acetone catalyzed by ytterbium(III) triflate [Yb(OTf)₃] in ionic liquids. The catalyst and ionic liquids can be easily recovered and reused, making this method friendly and environmentally acceptable.     

Fast Reductive Amination by Transfer Hydrogenation “on Water”

Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive amination in an aqueous phase is faster, and the molar ratio of the substrate to the catalyst (S/C) can be set as high as 1×10⁵, the highest S/C value ever reported in reductive amination reactions. The catalyst is easy to access and the reaction is operationally simple, allowing a wide range of ketones and aldehydes to react with various amines in high yields. The protocol provides a practical and environmental friendly new method for the synthesis of amine compounds.     

Versatile Iridicycle Catalysts for Highly Efficient and Chemoselective Transfer Hydrogenation of Carbonyl Compounds in Water

Cyclometalated iridium complexes are shown to be highly efficient and chemoselective catalysts for the transfer hydrogenation of a wide range of carbonyl groups with formic acid in water. Examples include α‐substituted ketones (α‐ether, α‐halo, α‐hydroxy, α‐amino, α‐nitrile or α‐ester), α‐keto esters, β‐keto esters and α,β‐unsaturated aldehydes. The reduction was carried out at substrate/catalyst ratios of up to 50 000 at pH 4.5 and required no organic solvent. The protocol provides a practical, easy and efficient way for the synthesis of β‐functionalised secondary alcohols, such as β‐hydroxyethers, β‐hydroxyamines and β‐hydroxyhalo compounds, which are valuable intermediates in pharmaceutical, fine chemical, perfume and agrochemical synthesis.     

优化迭代步长的两种改进增量谐波平衡法

增量谐波平衡法(IHB法)是一个半解析半数值的方法, 其最大优点是适合于强非线性系统振动的高精度求解. 然而, IHB法与其他数值方法一样, 也存在如何选择初值的问题, 如初值选择不当, 会存在不收敛的情况. 针对这一问题, 本文提出了两种基于优化算法的IHB法: 一是结合回溯线搜索优化算法(BLS)的改进IHB法(GIHB1), 用来调节IHB法的迭代步长, 使得步长逐渐减小满足收敛条件; 二是引入狗腿算法的思想并结合BLS算法的改进IHB法(GIHB2), 在牛顿-拉弗森(Newton-Raphson)迭代中引入负梯度方向, 并在狗腿算法中引入2个参数来调节BSL搜索方式用于调节迭代的方式, 使迭代方向沿着较快的下降方向, 从而减少迭代的步数, 提升收敛的速度. 最后, 给出的两个算例表明两种改进IHB法在解决初值问题上的有效性.      

Rh/SiO2催化剂上甲烷部分氧化制合成气的核磁共振研究

 利用1H MAS NMR技术,在甲烷部分氧化(POM)制合成气反应条件下研究了Rh/SiO2催化剂上氢与金属的相互作用及反应机理. 结果发现,氢气在Rh/SiO2上解离吸附后可能有四种存在形式: 化学位移为δ=-100～-120的可逆(αM)和不可逆(αI)吸附氢物种,δ=0～-100的“氢云”或“氢雾”形式的氢物种和δ=3.0的溢流氢物种. 溢流氢物种是由可逆吸附的氢物种和“氢云”或“氢雾”状态的氢物种溢流到SiO2上并弱吸附在桥式氧(Si-O-Si)附近而形成的. 溢流氢物种活化晶格氧,形成一种POM反应的活性氧物种OH-. 活性氧物种OH-反溢流到Rh上,并与CH4解离吸附在Rh上的CHx物种反应生成含氧中间物种CHxO. CHxO物种的化学位移为5～7. O2参与CHxO物种的进一步氧化,或补充溢流氢夺取桥式氧后形成的缺陷位上的晶格氧,在高温(973 K)反应条件下,O2可能优先补充缺陷位上的晶格氧,使CHx的氧化按表面反应机理进行.     

以双硫酯为链转移剂的活性自由基聚合

合成并研究了两种双硫酯链转移剂的纯化方法 ,进行了多种单体以双硫酯为链转移剂的活性自由基聚合及嵌段共聚 .发现以PhC(S)SC(CH3) 2 Ph为链转移剂的效果比PhC(S)SCH(CH3)Ph好 ,聚合产物的多分散性系数较小 .引发剂与链转移剂的摩尔数比为 1∶3 5～ 1∶4 2时 ,得到多分散性系数小 ,实测分子量与理论分子量相近的聚合产物 .聚合物的分子量随时间和转化率的增加而增加 ,加入第二单体形成嵌段共聚物 ,具有活性聚合特征 .聚甲基丙烯酸酯大分子引发剂引发丙烯酸酯单体聚合时 ,聚合速度最快 .