Manganese‐Catalyzed Dehydrogenative [4+2] Annulation of NH Imines and Alkynes by CH/NH Activation

Described herein is a manganese‐catalyzed dehydrogenative [4+2] annulation of N? H imines and alkynes, a reaction providing highly atom‐economical access to diverse isoquinolines. This transformation represents the first example of manganese‐catalyzed C? H activation of imines; the stoichiometric variant of the cyclomanganation was reported in 1971. The redox neutral reaction produces H₂ as the major byproduct and eliminates the need for any oxidants, external ligands, or additives, thus standing out from known isoquinoline synthesis by transition‐metal‐catalyzed C? H activation. Mechanistic studies revealed the five‐membered manganacycle and manganese hydride species as key reaction intermediates in the catalytic cycle.     

Gold‐Catalyzed Diastereoselective Cycloisomerization of Alkylidene‐Cyclopropane‐Bearing 1,6‐Diynes

An unprecedented gold‐catalyzed diastereoselective cycloisomerization of 1,6‐diynes bearing an alkylidene cyclopropane moiety has been developed. This methodology enables rapid access to a variety of 1,2‐trimethylenenorbornanes, which are important building blocks in the preparations of abiotic and sesquiterpene core structures.     

Restraint of the Differentiation of Mesenchymal Stem Cells by a Nonfouling Zwitterionic Hydrogel

The success of human mesenchymal stem cell (hMSC) therapies is largely dependent on the ability to maintain the multipotency of cells and control their differentiation. External biochemical and biophysical cues can readily trigger hMSCs to spontaneously differentiate, thus resulting in a rapid decrease in the multipotent cell population and compromising their regenerative capacity. Herein, we demonstrate that nonfouling hydrogels composed of pure poly(carboxybetaine) (PCB) enable hMSCs to retain their stem‐cell phenotype and multipotency, independent of differentiation‐promoting media, cytoskeletal‐manipulation agents, and the stiffness of the hydrogel matrix. Moreover, encapsulated hMSCs can be specifically induced to differentiate down osteogenic or adipogenic pathways by controlling the content of fouling moieties in the PCB hydrogel. This study examines the critical role of nonspecific interactions in stem‐cell differentiation and highlights the importance of materials chemistry in maintaining stem‐cell multipotency and controlling differentiation.     

β‐Functionalization of Carboxylic Anhydrides with β‐Alkyl Substituents through Carbene Organocatalysis

The first NHC‐catalyzed functionalization of carboxylic anhydrides is described. In this reaction, the β carbon behaves as a nucleophilic carbon and undergoes asymmetric reactions with electrophiles. Anhydrides with challenging β‐alkyl substituents work effectively.     

Synthesis,thermal, and photophysical properties of polymethylmethacryalte (PMMA) doped with ternary deuterated Eu(III) complexes

Two Eu(III) ternary luminescent complexes, Eu(tpb-H)₃(Tppo)₂ and Eu(tpb-H)₃(Topo)₂ (Tppo: triphenylphosphine oxide, Topo: trioctylphosphine oxide, tpb: 4,4,4-trifluoro-1-phenyl-1,3-butanedione) were synthesized using β-diketonates and phosphine oxides as ligands. Luminescent polymers were fabricated by incorporating the deuterated Eu(III) complexes in a PMMA matrix. Luminescent PMMA containing Eu(tpb-D)₃(Tppo)₂ exhibited relatively higher quantum yield, faster radiation rate, sharper red emission and larger stimulated emission cross-section and the results indicated prepared luminescent polymers including Eu(tpb-D)₃(Tppo)₂ showed promising results for applications in novel organic Eu(III) devices. Additionally, the Eu(III) complexes and luminescent PMMA showed good thermostabilization.     

含Ti的HMS介孔材料催化剂及其对丙烯环氧化催化性能的研究

分别用水热合成法和气相四氯化钛(TiCl4)接枝法制备了Ti-HMS和Ti/HMS催化剂.表征结果表明,经过气相TiCl4接枝后的样品依然保持HMS(Hexagonal Mesoporous Silica,缩写为HMS)介孔材料特征,钛(Ti)物种主要以四配位的活性位形式存在.经过甲基接枝处理的催化材料,增加了表面的疏水性.丙烯环氧化反应结果表明,SN-Ti/HMS具有更高的催化性能.在2 500 h的稳定试验中,过氧化氢异丙苯(CHP)转化率大于99.0%,环氧丙烷(PO)选择性大于96.0%.研究和优化了环氧化反应工艺条件.采用浓度为30%的CHP为原料,CHP重量空速为1.0 h-1,床层温度为100℃,反应压力为3.0 MPa.     

2-亚胺吡啶镍配合物的合成、晶体结构及催化乙烯聚合

经过一系列化学反应,在吡啶环上引入特丁基及甲醛基,再与2,6-二异丙基苯胺反应生成2-(N-2,6-二异丙基苯亚氨基)亚甲基-6-特丁基吡啶(g)配体,并合成了相应的配合物[NiBr2(g)](h)。配合物h的单晶结构表明其为单配体单金属结构,属于正交晶系,a=1.527 76(14)nm,b=1.608 46(15)nm,c=1.837 77(17)nm,晶胞体积4.516 0(7)nm3,Z=8。在助催化剂MAO的作用下,考察了催化乙烯聚合特性,在0℃时,所得聚合产物中包括支化聚合物和齐聚物,其中支化聚合物的分子量Mw=1.09×104,其支链大部分为甲基、丁基和长支链,支链密度为58.5。     

Multicomponent Reactions for Diverse Synthesis of N‐Substituted and NH 1,4‐Dihydropyridines

The multicomponent reactions of aldehydes, electron deficient alkynes and amines have been successfully performed to yield a number of symmetrical 2,6‐unsubstituted 1,4‐dihydropyridines (1,4‐DHPs). This method has been found generally applicable for the synthesis of both N‐substituted and N‐unsubstituted 1,4‐DHPs by employing secondary amine to activate the alkyne component via enaminoester intermediates. The present method runs through an enamine type activation, which is different from the known approach employing AcOH as solvent.     

Capillary electrophoresis with laser-induced fluorescence detection of main polyamines and precursor amino acids in saliva

A hollow-fiber liquid-phase microextraction （HF-LPME） method has been developed for the purification and preconcentration of biogenic polyamines and their precursor amino acids in human saliva. Putrescine （Put）, cadaverine （Cad）, spermidine （Spe）, ornithine （Orn）, lysine （Lys）, and arginine （Arg） were determined by the CE-LIF detection after microextraction. Several factors that affect extraction efficiency, separation, and detection were investigated. Under the optimum conditions, six analytes could achieve baseline separation within 30 min, exhibiting a linear calibration at three orders of magnitude （r2 〉 0.998）; the obtained enrichment factors of HF-LPME were between 19 （for Orn） and 2] 8 （for Cad）, and the LODs were in the range of 0.0072-0.26 nmol/L. The proposed HF-LPME/CE-LIF method has been successfully applied for the sensitive analyses of the real-world saliva samples collected from healthy volunteers and different patients with oral diseases, providing a potential method for primary non-invasive diagnosis of some oral diseases.     

Asymmetric catalytic anhydride openings via carbon-based nucleophiles

The asymmetric desymmetrization of cyclic anhydrides via the addition of carbon-based nucleophiles has been the focus of considerable levels of interest because it leads to optically active products. Over the past 20 years, a variety of different catalytic asymmetric alkylation reactions have been developed for the desymmetrization of cyclic anhydrides using different metal reagents as nucleophiles and using chiral ligands. The purpose of this review is to provide an overview of significant developments in this field. ~ 2013 Fen-Er Chen. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.