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Chemistry 2021 Aug 29;27(47):12069-12077. Epub 2021 Jul 29.

National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan.

Recent advances in surface organometallic chemistry have enabled the detailed characterization of the surface species in single-site heterogeneous catalysts. However, the selective formation of bis-grafted surface species remains challenging because of the heterogeneity of the supporting surface. Herein, we introduce a metal complex bearing bidentate disilicate ligands, -OSi(O Bu) OSi(O Bu) O-, as a molecular precursor, which has a silicate framework adjacent to the metal (Pt) center. Read More

Chemistry 2021 Mar 12;27(15):4789-4816. Epub 2021 Jan 12.

Centro Singular de Investigación en Química Biolóxica e Materiais, Moleculares (CIQUS) and Departamento de Química Orgánica, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain.

During the last decade, there has been a tremendous interest for developing non-natural biocompatible transformations in biologically relevant media. Among the different encountered strategies, the use of transition metal complexes offers unique possibilities due to their high transformative power. However, translating the potential of metal catalysts to biological settings, including living cells or small-animal models such as mice or zebrafish, poses numerous challenges associated to their biocompatibility, and their stability and reactivity in crowded aqueous environments. Read More

Chemistry 2020 Nov 18;26(66):15052-15064. Epub 2020 Sep 18.

Key Laboratory of Green Chemistry & Technology of Ministry of, Education, College of Chemistry, Sichuan University, Chengdu, 610064, P. R. China.

Over the past decades, organometallic complexes with precious elements, such as ruthenium and iridium, are widely used as visible-light photoredox catalysts. Recently, more and more complexes based on earth-abundant and inexpensive elements have been used as sensitizers in photochemistry. Although the photoexcited state lifetimes of iron complexes are typically shorter than those of traditional photosensitizers, the utilization of iron catalysts in photochemistry has sprung up owing to their abundance, low price, nontoxicity, and novel properties, including exhibiting ligand to metal charge transfer states. Read More

Chemistry 2019 Dec 9;25(71):16382-16389. Epub 2019 Dec 9.

Institut für Organische und Biomolekulare Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077, Göttingen, Germany.

Despite major advances, organometallic C-H transformations are dominated by precious 5d and 4d transition metals, such as iridium, palladium and rhodium. In contrast, the unique potential of less toxic Earth-abundant 3d metals has been underexplored. While iron is the most naturally abundant transition metal, its use in oxidative, organometallic C-H activation has faced major limitations due to the need for superstoichiometric amounts of corrosive, cost-intensive DCIB as the sacrificial oxidant. Read More

Chemistry 2018 Feb 21. Epub 2018 Feb 21.

Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology, Meilong Road No. 130, Shanghai, 200237, P. R. China.

During the past decades, cycloisomerizations of methylenecyclopropanes using gold catalysis have attracted much attention from organic chemists. The different patterns of gold(I)-catalyzed cycloisomerizations of methylenecyclopropanes have been developed, and they can be classified as ring-opening and ring-expansion reaction patterns. This synthetic methodology provides a new approach to novel cyclic- or polycyclic compounds. Read More

Chemistry 2017 Dec 26;23(68):17157-17165. Epub 2017 Oct 26.

Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074, Aachen, Germany.

The advances made in the mechanosynthesis of inorganic and organometallic complexes and the excellent past developments with metal-catalyzed cross-coupling reactions by high-speed ball milling have sufficienly laid the ground work for the merging of C-H functionalization and mechanochemical techniques. In recent years, the fast development of mechanochemical C-H activation have given us examples of metal-catalyzed olefinations, amidations, halogenations, and oxidative couplings, among others. This concept article will describe some of the events that led to the development of mechanochemical C-H activation, the current state-of-the-art, the present challenges of this merge, and some unique scenarios in which mechanochemistry could complement the traditional solution-based approaches. Read More

Chemistry 2017 Apr 16;23(20):4741-4749. Epub 2017 Feb 16.

Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259 Nagatsuta Midori-ku, Yokohama, 226-8503, Japan.

Recent developments of single-molecule conductance measurements allow us to understand fundamental conducting properties of molecular wires. While a wide variety of organic molecular wires have been studied so far, inorganic and organometallic molecular wires have received much less attention. However, molecular wires with transition-metal atoms show interesting features and functions distinct from those of organic wires. Read More

Chemistry 2017 01 10;23(3):467-512. Epub 2016 Oct 10.

Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, 3663 N. Zhongshan Road, Shanghai, 200062, P. R. China.

In the past decade, there have been many extraordinary advances in the development of gold-catalyzed enantioselective annulations, such as cycloadditions, cyclizations, cycloisomerizations, and tandem annulations, which are of particular interest owing to their potential for rapid construction of optically active hetero- and carbocyclic molecules. This Review summarizes the methods to construct chiral cyclic compounds by gold-catalyzed enantioselective annulations reported since 2005. The Review is organized according to the general annulation types catalyzed by chiral gold complexes or chiral gold salts, which have four main types (cycloadditions, cyclizations of C-C multiple bonds with tethered nucleophiles, cycloisomerization or cyclization of enynes, and tandem annulations), as well as some other strategies. Read More

Chemistry 2016 Dec 13;22(50):17910-17924. Epub 2016 Jul 13.

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.

In recent years, α-imino rhodium carbene complexes derived by ring-opening of N-sulfonyl-1,2,3-triazoles have attracted much attention from organic chemists. Many transformations of these species have been reported that involve, in most cases, nucleophilic attack at the carbene center of the α-imino rhodium carbene, facilitating the synthesis of a wide range of novel and useful compounds, particularly heterocycles. This Minireview mainly focuses on advances in the transformation of N-sulfonyl-1,2,3-triazoles during the past two years. Read More

Chemistry 2016 Aug 5;22(34):11918-33. Epub 2016 Jul 5.

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P. R. China.

Recent advances in dearomatization through halofunctionalization reactions are summarized in this Minireview. Two general categories of strategies are currently employed in this field. On one hand, the reaction can be initiated with electrophilic halogenation at an alkyne or alkene moiety. Read More

Chemistry 2016 May 18;22(19):6432-57. Epub 2016 Mar 18.

Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química, Avanzada (ORFEO-CINQA), Universidad de Sevilla and Consejo Superior de Investigaciones Cientificas (CSIC), Avenida Américo Vespucio 49, 41092, Sevilla, Spain.

Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition-metal complexes containing M-CH3 fragments. Read More

Chemistry 2015 Jul 9;21(29):10278-88. Epub 2015 Apr 9.

State Key Laboratory for Physical Chemistry of Solid Surfaces and The Key Laboratory for Chemical Biology of Fujian Province, Department of Chemistry, Xiamen University, Xiamen, 361005, Fujian (P. R. China).

Fluorenes are a commonly encountered structural motif in materials science, pharmaceutical chemistry, and organic synthesis. Among various strategies towards the synthesis of this unique structure, transition metal-catalyzed functionalization has emerged as one of the most efficient methods. This Minireview presents an overview of the recent advances in this emerging area by highlighting the reactions' specificity and applicability and, where possible, provides a mechanistic rationale. Read More

Chemistry 2014 Dec 21;20(51):16806-29. Epub 2014 Oct 21.

Departamento de Química Orgánica, Facultad de Farmacia y Bioquímica, Universidad de Buenos Aires, Junín 954 CP1113-Buenos Aires, Argentina, Fax: (+54) 11-4964-8350.

Electrophilic trifluoromethylation reactions have been the latest approach to achieve the fluoroalkylation of compounds with newly-discovered reagents, such as the Togni's (1-trifluoromethyl-1,2-benziodoxol-3-(1 H)-one), Umemoto's (S-(trifluoromethyl)dibenzothiophenium tetrafluoroborate), Yagupolskii's (S-(trifluoromethyldiarylsulfonium salts), Shreeve's (S-(trifluoromethyl)dibenzothiophenium triflate), and Shibata's (trifluoromethylsulfoximine salts) reagents. All these reagents produce an electrophilic trifluoromethylating (CF3 (+) ) species that undergoes reaction with nucleophiles. In addition, these latter reactive species (i. Read More

Chemistry 2013 Sep 19;19(40):13492-503. Epub 2013 Aug 19.

WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL (UK).

Most recent advances in metallation chemistry have centred on the bulky secondary amide 2,2,6,6-tetramethylpiperidide (TMP) within mixed metal, often ate, compositions. However, the precursor amine TMP(H) is rather expensive so a cheaper substitute would be welcome. Thus this study was aimed towards developing cheaper non-TMP based mixed-metal bases and, as cis-2,6-dimethylpiperidide (cis-DMP) was chosen as the alternative amide, developing cis-DMP zincate chemistry which has received meagre attention compared to that of its methyl-rich counterpart TMP. Read More

Chemistry 2012 Dec 14;18(51):16258-71. Epub 2012 Nov 14.

School of Chemistry, University of Dublin, Trinity College, Dublin 2, Ireland.

The chemistry of the uranyl ion ([UO(2)](2+)) has evolved remarkably over the past few years, with unexpected reactivity observed that challenge our understanding of this ion, and of actinides in general. This review highlights some recent advances in the field, focussing on the organometallic chemistry of the uranyl moiety, which is not well developed in comparison to lower oxidation states of uranium. The use of uranyl as a catalyst is highlighted and the newly developed supramolecular chemistry is described. Read More

Chemistry 2012 Jan;18(4):1030-7

Laboratory for Nanomaterials, National Center for Nanoscience and Technology, Beijing 100190, P.R. China.

Nature bestows many gifts upon us, among which countless biomolecules have the ability to bridge metal ions and exert the important function in biology. By taking advantage of specific interactions between metal ions and biomolecules, this article highlights a novel concept for construction of nanoscale biocoordination polymers through replacement of synthetic organic molecules with natural biomolecules as building blocks. The most recent advances are summarized and future challenges are discussed. Read More

Chemistry 2011 Oct 6;17(42):11789-96. Epub 2011 Sep 6.

Institut für Organische Chemie und Biochemie, Freiburg Institute for Advances Studies (FRIAS), Universität Freiburg, Albertstr. 21, Germany.

Stereoselective and diversity-oriented synthesis of trisubstituted olefins was achieved by using ortho-diphenylphosphanyl benzoate (o-DPPB) as a directing group for allylic substitution. The starting point of this methodology was a set of α-methylene aldehydes derived from Baylis-Hillman adducts. Subsequent addition of different organometallic reagents led to a variety of allylic alcohol substrates. Read More

Chemistry 2011 Apr 1;17(16):4470-9. Epub 2011 Mar 1.

WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL UK.

Building on recent advances in synthesis showing that the addition of inorganic salts to Grignard reagents can greatly enhance their performance in alkylation reactions to ketones, this study explores the reactions of EtMgCl with benzophenone in the presence of stoichiometric or catalytic amounts of ZnCl(2) with the aim of furthering the understanding of the role and constitution of the organometallic species involved in these transformations. Investigations into the metathesis reactions of three molar equivalents of EtMgCl with ZnCl(2) led to the isolation and characterisation (X-ray crystallography and (1)H and (13)C NMR spectroscopy) of novel magnesium "zinc-rich" zincate [{(THF)(6)Mg(2)Cl(3)}(+){Zn(2)Et(5)}(-)] (1), whose complicated constitution in THF solutions was assessed by variable-temperature (1)H DOSY NMR studies. Compound 1 reacted with one equivalent of benzophenone to yield magnesium magnesiate [{(THF)(6)Mg(2)Cl(3)}(+){Mg(2)(OC(Et)Ph(2))(2)Cl(3)(THF)}(-)] (3), whose structure was determined by X-ray crystallography. Read More

Chemistry 2007 ;13(3):736-44

Departamento de Química Orgánica, Facultad de Química, Universidad Complutense, 28040 Madrid, Spain.

The knowledge of the reactivity of Fischer carbene complexes in electron transfer processes is still in the early stage of development, but interesting advances are foreseeable in this young branch of metal-carbene chemistry. Although these compounds have a dual reactivity (which makes them good substrates for oxidation and reduction processes), their behavior towards chemical electron transfer (ET) reagents was unknown until very recently. This article covers the progress accomplished in the reactivity of these compounds towards chemical ET reagents (C(8)K or SmI(2)), as well as the use of nonconventional sources of electrons, such as electrospray ionization (ESI) to induce ET processes. Read More

Chemistry 2006 Jun;12(19):4954-63

Department of Chemistry, University of Illinois, Urbana, IL 61801, USA.

This paper chronicles the conceptual development, proof of principle experiments, and recent advances in the palladium-catalyzed cross-coupling reactions of the conjugate bases of organosilanols. The discovery that led to the design and refinement of this process represents a classical illustration of how mechanistic studies can provide a fertile ground for the invention of new reactions. On the basis of a working hypothesis (which ultimately proved to be incorrect) and the desire to effect silicon-based cross-coupling without the agency of fluoride activation, a mild and practical palladium-catalyzed cross-coupling of alkenyl-, aryl-, and heteroaryl silanolates has been developed. Read More