Copper(I) Oxide Catalyzed Formation of C?S Bond Mediated by N,N′‐Type Ligand

1,10‐Phenanthroline, a simple and cheap N,N′‐type ligand, was found to work well as the ligand of C? S coupling catalyzed by Cu₂O. The corresponding coupling products were synthesized in good to excellent yields (75%–99%) in DMSO at 80°C. A variety of aryl halides and thiols were investigated and satisfactory results were obtained.     

Heterograft copolymers via double click reactions using one‐pot technique

The double click reactions (Cu catalyzed Huisgen and Diels–Alder reactions) were used as a new strategy for the preparation of well‐defined heterograft copolymers in one‐pot technique. The synthetic strategy to the various stages of this work is outlined: (i) preparing random copolymers of styrene (St) and p‐chloromethylstyrene (CMS) (which is a functionalizable monomer) via nitroxide mediated radical polymerization (NMP); (ii) attachment of anthracene functionality to the preformed copolymer by the o‐etherification procedure and then conversion of the remaining ? CH₂Cl into azide functionality; (iii) by using double click reactions in one‐pot technique, maleimide end‐functionalized poly(methyl methacrylate) (PMMA‐MI) via atom transfer radical polymerization (ATRP) of MMA and alkyne end‐functionalized poly (ethylene glycol) (PEG‐alkyne) were introduced onto the copolymer bearing pendant anthryl and azide moieties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6969–6977, 2008     

Ullmann CO coupling of sterically hindered secondary alcohols using excess amount of strongly coordinating monodentate ligands

A new effective copper catalyzed CO coupling reaction using excess amount of strongly coordinating monodentate ligands was successfully developed. Among the DMAP-type monodentate ligands, 4-pyrrolidinopyridine afforded the best results. The developed reaction is widely applicable for the synthesis of various hindered or acyclic secondary alkyl-aryl ethers. In this study, a novel and remarkable acceleration of the coupling reaction using excess amount of monodentate ligands was discovered.     

Base-catalyzed cross coupling of secondary alcohols and aryl-aldehydes with concomitant oxidation of alcohols to ketones: An alternative route for synthesis of the Claisen-Schmidt condensation products

Base-catalyzed C–C cross coupling of secondary alcohols and aryl-aldehydes was achieved, when an alcoholic solution of an aryl-aldehyde was stirred under reflux for 45 h in the presence of a catalytic (20 mol%) amount of K₂CO₃. The consistent formation of α,α′-bis-(benzylidene) alkanones was obtained in moderate to good yields using various secondary alcohols and substituted aryl-aldehydes. Herein, α,α′-bis-(benzylidene)alkanones, which are the classical products of Claisen-Schmidt (cross aldol) condensation, have been synthesized via an alternative strategy using secondary alcohols. Bis-(benzylidene) alkanones are an integral part of various drug regimes and the production of bis-(benzylidene) alkanones without using any precious metal is a major outcome of the present reaction.     

铁掺杂的高比表面二氧化硅的制备及其苯酚降解性能

研究了以聚乙二醇为模板剂、正硅酸乙酯(TEOS)为硅源制备铁掺杂的多孔二氧化硅的方法。开发了一步完成多孔材料制备和掺杂的新工艺。研究了不同的铁元素掺杂量对样品性能的影响。采用低温氮吸附、SEM、FTIR、XRD方法表征了样品的比表面、孔结构和表面基团等信息。最优样品比表面大于700 m²·g^-1、孔容大于1 mL·g^-1。研究了所制备的多孔材料和双氧水共同降解水中苯酚的能力,研究发现负载铁的催化剂可以在很宽的pH值范围内(3~8)和双氧水协同使用,这可能是因为铁元素被牢固负载于多孔二氧化硅的骨架上,避免了其在高pH值下发生的水解反应。     

Synthesis and characterization of polymer linked copper(I) bis(N‐heterocyclic carbene) mechanocatalysts

In this paper, the synthesis and characterization of a series of latent polymeric bis(N‐heterocyclic carbene) (NHC) copper(I) complexes is reported, which can be activated for the copper(I)‐catalyzed azide/alkyne cycloaddition (CuAAC) via ultrasound. To prove the influence of chain length and nature of the polymer towards the activation, poly(isobutylene) (PIB), poly(styrene) (PS) and poly(tetrahydrofuran) (PTHF) are synthesized via living polymerization techniques (LCCP, ATRP, CROP) obtaining different chain lengths (from 2500 to 9000 g/mol), followed by quaternization with N‐methylimidazole, generating the corresponding N‐methylimidazolium‐telechelic polymers. The deprotonation of these macroligands via strong bases like sodium tert‐butoxide (NaO^tBu) or potassium hexamethyldisilazide (KHMDS) yields the free N‐heterocyclic carbenes (NHCs), which are used to coordinate to tetrakis(acetonitrile)copper(I) hexafluorophosphate, forming the final polymer‐based mono‐ and bis(N‐methylimidazole‐2‐ylidene) copper(I)X complexes. The structural proof of these complexes is accomplished via ¹H‐NMR spectroscopy, MALDI‐TOF‐MS and GPC‐techniques. The activation of the copper(I) biscarbene catalysts by ultrasound is studied by GPC, revealing the cleavage of one shielding NHC‐ligand. The initial catalytic latency and the via ultrasound introduced catalytic activation is successfully demonstrated monitoring a CuAAC “click” reaction of benzyl azide and phenylacetylene by in situ ¹H‐NMR spectroscopy introducing thus “click” conversions up to 97%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3893–3907     

An improved general method for palladium catalyzed alkenylations and alkynylations of aryl halides under microwave conditions

Palladium catalyzed facile method for alkenylation and alkynylation of arylhalides in good to excellent yield under microwave condition is reported.     

Towards Stereoselective Synthesis of the C(31)–C(39) and C(20)–C(27) Fragments of Phorboxazole A

The stereoselective synthesis of the C(31)–C(39) and C(20)–C(27) fragments of phorboxazole A ( 1 ) was achieved from commercially available and inexpensive D ‐mannitol. Crimmins aldol reaction and a decarboxylative Claisen‐type reaction are the key steps for the C(31)–C(39) fragment, and L ‐proline‐catalyzed aldol reaction, Sharpless asymmetric epoxidation, and epoxide ring opening reaction with Gilman's reagent are the key steps for the C(20)–C(27) fragment of phorboxazole.     

Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries

A novel route for the synthesis of poly(ethylene glycol)‐b‐polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one‐pot procedure under near‐visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1⁻¹ and a polydispersity index of 1.20.

     

A UV‐Cleavable Bottlebrush Polymer with o‐Nitrobenzyl‐Linked Side Chains

An ultraviolet (UV)‐cleavable bottlebrush polymer is synthesized using the “grafting‐onto” strategy by combining living radical polymerization and copper‐catalyzed azide‐alkyne cycloaddition (CuAAC). In this approach, reversible addition‐fragmentation chain transfer polymerization is used to prepare a poly(methylacrylate) backbone with azide side groups, while atom transfer radical polymerization is employed to prepare polystyrene (PS) side chains end‐functionalized with o‐nitrobenzyl (UV‐cleavable) propargyl groups. CuAAC is then used to graft PS side chains onto the polymer backbone, producing the corresponding bottlebrush polymers with UV‐cleavable PS side chains. The formation of the bottlebrush polymer is characterized by ¹H nuclear magnetic resonance spectroscopy, gel permeation chromatography (GPC), and Fourier transform infrared spectroscopy. The cleavage behavior of the bottlebrush polymer is monitored in tetrahydrofuran solution under UV irradiation by GPC and viscosity measurements.