Colloidal cobalt nanoparticles: a highly active and reusable Pauson-Khand catalyst

A new Pauson-Khand catalyst based on colloidal cobalt nanoparticles has been developed; the catalyst is highly effective for many intra- and inter-molecular Pauson-Khand reactions and can be recycled and reused many times without losing catalytic activity.     

Phosphine dendrimer-stabilized palladium nanoparticles, a highly active and recyclable catalyst for the Suzuki-Miyaura reaction and hydrogenation

[reaction: see text] Phosphine dendrimer-stabilized palladium nanoparticles were synthesized and found to be highly effective for Suzuki coupling reactions, affording good to excellent product yields, high turnover number (up to 65,000), and excellent reusability (up to 9 catalytic runs). Furthermore, these Pd nanoparticles are efficient and selective catalysts for hydrogenations.     

Tetramethylnorbornadiene, a versatile alkene for cyclopentenone synthesis through intermolecular Pauson-Khand reactions

1,2,3,4-Tetramethyl-bicyclo[2.2.1]hepta-2,5-diene (TMNBD, for tetramethylnorbornadiene) has been prepared and used successfully as an acetylene equivalent in the synthesis of substituted cyclopentenones. TMNBD is easily accessible on a multigram scale and displays excellent reactivity toward the intermolecular Pauson-Khand reaction. Conjugate additions on the resulting tricyclic compounds proceed with exquisite diastereoselectivity. The retro-Diels-Alder reaction of these TMNBD derivatives occurs under much smoother conditions than those required for its norbornadiene homologues.     

Pd on amine-terminated ferrite nanoparticles: a complete magnetically recoverable facile catalyst for hydrogenation reactions

[structure: see text]. The present communication reports a facile route for Pd(0) immobilization on the surface of amine-terminated Fe3O4 and NiFe2O4 nanoparticles for a series of hydrogenation reactions. The catalysts are completely recoverable with the simple application of an external magnetic field, and the efficiency of the catalyst remains unaltered even after 10 repeated cycles for each of the reactions.     

On early events in the Pauson-Khand reaction

[reaction: see text]. The Magnus Pauson-Khand (PK) mechanism has been studied for the first time by electrospray ionization coupled to tandem mass spectrometry. It has been found that loss of CO from the PK complex precedes olefin coordination and insertion.     

氮掺杂碳包覆纳米钴颗粒用于硝基芳烃室温选择性加氢（英文）

通过硝基芳烃选择性加氢能高效地制备芳香胺和环胺,其中芳香胺作为重要的化工中间体应用于多个领域(精细化工、商业产品和聚合物).在加氢反应过程中,硝基的还原伴随着生成一些副产物(如亚硝基和偶氮化合物).同时对于含还原性基团的取代硝基苯,硝基的选择还原也面临着很大的挑战.金属钴是常用的硝基加氢催化剂活性成分,但是由于对反应底物的过度吸附,导致其选择性不高.早期研究发现,氮掺杂碳催化剂能有效吸附硝基基团,从而在硝基苯加氢中表现出一定活性,但对分子氢的活化不足.因此,氮掺杂碳作为吸附材料与钴构建复合催化剂,能够发挥吸附和活化氢的协同作用,从而高效催化硝基苯加氢.基于此,本课题组发展了一种制备方法,可将钴颗粒尺寸限制在10 nm左右,且包覆在氮掺杂碳中,并应用于对硝基苯酚的室温选择性加氢反应中,发现相较于碳负载钴和氮掺杂碳催化剂,所制催化剂在室温下表现出了很好的活性和选择性.在此基础上,本文采用元素分析、X射线光电子能谱(XPS)和拉曼光谱(Raman)等手段对催化剂形貌和结构进行了研究.表征结果表明,保持钴前驱体的量不变,随着氮化碳加入量的增加,催化剂中氮掺杂浓度提高;当氮化碳/钴1时,氮掺杂浓度不变.红外结果表明,与普通碳载体相比,氮掺杂碳对硝基苯有很强的吸附作用,而氮掺杂碳包覆的钴催化剂也表现出同样的结果.通过调节氮的掺杂浓度,一方面可以修饰碳载体的电子结构,增加表面缺陷的浓度,提高与反应底物的相互作用;另一方面可以促进电子由钴颗粒转移至与之相连的氮原子上,因此进一步促进钴颗粒对分子氢的活化作用.该复合结构的催化剂实现了底物吸附和氢活化的协同作用,氮掺杂碳将反应底物吸附在表面,钴颗粒活化氢,随后解离的氢原子与表面吸附物反应,从而实现硝基苯的高效加氢.其中Co@NC-1催化活性最高,并在循环套用10次后,仍维持较高的催化活性,同时对含其它取代基的硝基苯均表现很高的活性和选择性.     

Enone-alkyne reductive coupling: a versatile entry to substituted pyrroles

The reductive coupling of enones or enals with alkynes, followed by olefin oxidative cleavage and Paal-Knorr cyclization, provides a versatile entry to a variety of pyrrole frameworks. A number of limitations of alternate entries to the requisite 1,4-dicarbonyl intermediate are avoided. Classes of pyrroles that are accessible by this approach include 2,3-, 2,4-, 1,2,3-, 1,2,4-, 2,3,5-, and 1,2,3,5-substituted monocyclic pyrroles as well as a number of fused-ring polycyclic derivatives.     

Titania-silver and alumina-silver composite nanoparticles: novel, versatile synthesis, reaction mechanism and potential antimicrobial application

Titania-silver (TiO(2)-Ag) and alumina-silver (Al(2)O(3)-Ag) composite nanoparticles were synthesised by a simple, reproducible, wet chemical method under ambient conditions. The surface of the oxides was modified with oleic acid, which acted as an intermediate between the oxide surface and the silver nanoparticles. The resulting composite nanoparticles were thoroughly characterised by XRD, TEM, XPS, FTIR and TGA to elucidate the mode of assembly of Ag nanoparticles on the oxide surfaces. Epoxy nanocomposites were formulated with TiO(2)-Ag and Al(2)O(3)-Ag to examine potential applications for the composite nanoparticles. Preliminary results from disc diffusion assays against Escherichia coli DH5α and Staphylococcus epidermidis NCIMB 12721 suggest that these TiO(2)-Ag and Al(2)O(3)-Ag composite nanoparticles have potential as antimicrobial materials.     

A versatile Ru catalyst for the asymmetric transfer hydrogenation of both aromatic and aliphatic sulfinylimines

A highly efficient Ru catalyst based on an achiral, very simple, and inexpensive amino alcohol ligand (2‐amino‐2‐methylpropan‐1‐ol) has been developed for the asymmetric transfer hydrogenation (ATH) of chiral N‐(tert‐butylsulfinyl)imines. This complex is able to catalyze the ATH of both aromatic and the most challenging aliphatic sulfinylimines by using isopropyl alcohol as the hydrogen source. The diastereoselective reduction of aromatic, heteroaromatic, and aliphatic sulfinylketimines, including sterically congested cases, over short reaction times (1–4 h), followed by desulfinylation of the nitrogen atom, affords the corresponding highly enantiomerically enriched (ee up to >99 %) α‐branched primary amines in excellent yields. The same ligand was equally effective for the synthesis of both (R)‐ and (S)‐amines by using the appropriate absolute configuration in the iminic substrate. DFT mechanistic studies show that the hydrogen‐transfer process is stepwise. Moreover, the origin of the diastereoselectivity has been rationalized.     

Arene-chromium tricarbonyl complexes in the Pauson-Khand reaction

[reactions: see text] We show the use of arene-chromium tricarbonyl complexes in intra- and intermolecular Pauson-Khand reactions. Both styrene and ethynylbenzene complexes react with alkynes and olefins. The synthesis of enynes connected through chromium-complexed aromatic rings is developed. The intramolecular Pauson-Khand reaction occurs in a totally diastereoselective manner.     

Tandem Pauson-Khand reaction and Diels-Alder reaction for access to polycycles in a one-pot reaction

Starting from easily available cyclic alkenes, enynes, and dienophiles, a tandem intermolecular Pauson-Khand reaction and Diels-Alder reaction yields polycyclic compounds in high yields.     

Metal nanoparticles immobilized on ion-exchange resins:A versatile and effective catalyst platform for sustainable chemistry

This paper reviews the recent achievements in the immobilization of metal nanoparticles on ion-exchange resins and the related catalytic application. The focus is on the production processes for fine and commodity chemicals for which a low environmental impact has been demonstrated. The most significant papers that appeared in the literature from January 2010 to July 2014 have been covered. Their uses in unselective processes, bulk chemicals production, fuel cells compo-nents, as well as the use of metal-free ion-exchange resins in acid/base-catalysed reactions, were not included.     

N-phosphino-p-tolylsulfinamide ligands: synthesis, stability, and application to the intermolecular Pauson-Khand reaction

Here we synthesized a family of racemic and optically pure N-phosphino-p-tolylsulfinamide (PNSO) ligands. Their stability and coordination behavior toward dicobalt-alkyne complexes was evaluated. Selectivities of up to 3:1 were achieved in the ligand exchange process with (mu-TMSC2H)Co2(CO)6. The resulting optically pure major complexes were tested in the asymmetric intermolecular Pauson-Khand reaction and yielded up to 94% ee. X-ray studies of the major complex 18a indicated that the presence of an aryl group on the sulfinamide reduces the hemilabile character of the PNSO ligands.     

Advances in the Pauson-Khand reaction: development of reactive cobalt complexes

Three conceptually new methods employing reactive cobalt carbonyl complexes have been developed for the Pauson-Khand reaction. The first method involves activation of alkyne-dicobalt hexacarbonyls with "hard" Lewis bases. Primary amines dramatically promote the stoichiometric Pauson-Khand reaction. The active cobalt complexes produced in the system exhibit high reducing ability. The second method involves activation of dicobalt octacarbonyl with less electron-donating "hard" Lewis bases such as 1,2-dimethoxyethane and water. These Lewis bases were successfully utilized as a promoter for the catalytic Pauson-Khand reaction. The third method employs methylidynetricobalt nonacarbonyl cluster, which exhibits high reactivity in the catalytic Pauson-Khand reaction in the absence of activator. This may be due to facile coordination of the substrate to the metal center through dissociative and associative mechanisms and/or cleavage of one of the cobalt-cobalt bonds.