Matthias Beller

Bio: Matthias Beller is an academic researcher from University of Rostock. The author has contributed to research in topics: Catalysis & Aryl. The author has an hindex of 113, co-authored 733 publications receiving 46344 citations. Previous affiliations of Matthias Beller include Technische Universität München & Ludwig Maximilian University of Munich.

Using carbon dioxide as a building block in organic synthesis

Abstract: Carbon dioxide exits in the atmosphere and is produced by the combustion of fossil fuels, the fermentation of sugars and the respiration of all living organisms. An active goal in organic synthesis is to take this carbon--trapped in a waste product--and re-use it to build useful chemicals. Recent advances in organometallic chemistry and catalysis provide effective means for the chemical transformation of CO₂ and its incorporation into synthetic organic molecules under mild conditions. Such a use of carbon dioxide as a renewable one-carbon (C1) building block in organic synthesis could contribute to a more sustainable use of resources.

Metal-Initiated Amination of Alkenes and Alkynes.

Abstract: The catalytic production of organic molecules is one of the most important applications of organometallic chemistry. For this purpose the distinct reaction chemistry of organic ligands covalently bound to transition metals is exploited. Most organometallic chemistry has focused on the formation of carboncarbon or carbon-hydrogen bonds. The platinum group metals, in particular Pd and Rh, have been the most commonly used elements insfrequently commercializedscatalytic processes that include hydrogenation, hydroformylation and others. On the other hand, carbon-oxygen and carbon-nitrogen bonds are found in the majority of organic molecules and are of particular importance in physiologically active substances. However, catalytic organometallic reactions that lead to the formation of carbonheteroatom bonds are less common.1,2 The catalytic construction of carbon-nitrogen bonds in amines is particularly rare.3-10 Clearly, efficient catalytic routes to nitrogen based molecules are of great interest.11 Especially useful are catalytic hydroaminations of olefins and alkynes which avoid production of byproducts, like salts, generally observed in metal-catalyzed aminations of C-X derivatives (X ) e.g., halogen). However, known aminations of olefins often require stoichiometric use of transition metals and general methods for carrying out aminations catalytically are not yet available.12,13 Most of the present enantioselective syntheses of molecules bearing an amine functionality use classical stoichiometric reactions with chiral auxiliaries or utilize enantiomerically pure starting material.14-16 Hydroamination of alkenes and alkynes, which constitutes the formal addition of a N-H bond across a carbon-carbon multiple bond (Scheme 1), is a transformation of seemingly fundamental simplicity and would appear to offer the most attractive route to numerous classes of organo-nitrogen molecules such as alkylated amines, enamines or imines. Organic chemists have developed various synthetic approaches for the amination of olefins.17-19 Direct addition of nucleophiles H-NR2 to activated alkenes is of general importance for the synthesis of compounds with nitrogen atoms â to groups such as keto, ester, nitrile, sulfoxide, or nitro.13,20-23 These additions usually lead to the anti-Markovnikov products. On the other hand aliphatic olefins as well as most aromatic olefins are often aminated to give the Markovnikov product. One possibility to reverse the reactivity of aliphatic olefins is the use of electrophilic nitrogen radicals which have been used to obtain anti-Markovnikov products.24 In the past much work has been done on the activation of alkenes with stoichiometric amounts of metal.24 Reactions are mostly promoted by complexes of titanium,25 iron,26 zirconium,27 palladium28-31 and mercury.32,33 However, catalytic additions of amines H-NR2 to nonactivated double or triple bonds are still rare. Two basic approaches have been employed to catalytically effect aminations and involve either alkene/alkyne or amine activation routes (Scheme 2).34,140 Alkene activation is generally accomplished with late-transition-metal catalysts, which render coordinated olefins more susceptible to attack by † Dedicated to Dipl. Chem. Martin Eichberger (deceased 11/20/ 1997). 675 Chem. Rev. 1998, 98, 675−703

Recent Applications of Palladium-Catalyzed Coupling Reactions in the Pharmaceutical, Agrochemical, and Fine Chemical Industries

Abstract: Palladium-catalyzed coupling reactions have become a central tool for the synthesis of biologically active compounds both in academia and industry. Most of these transformations make use of easily available substrates and allow for a shorter and more selective preparation of substituted arenes and heteroarenes compared to non-catalytic pathways. Notably, molecular-defined palladium catalysts offer high chemoselectivity and broad functional group tolerance. Considering these advantages, it is not surprising that several palladium-catalyzed coupling reactions have been implemented in the last decade into the industrial manufacture of pharmaceuticals and fine chemicals. In this review different examples from 2001-2008 are highlighted, which have been performed at least on a kilogram scale in the chemical and pharmaceutical industries.

Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality.

Abstract: Pick your Pd partners: A number of catalytic systems have been developed for palladium-catalyzed CH activation/CC bond formation. Recent studies concerning the palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle are discussed (see scheme), and the versatility and practicality of this new mode of catalysis are presented. Unaddressed questions and the potential for development in the field are also addressed. In the past decade, palladium-catalyzed CH activation/CC bond-forming reactions have emerged as promising new catalytic transformations; however, development in this field is still at an early stage compared to the state of the art in cross-coupling reactions using aryl and alkyl halides. This Review begins with a brief introduction of four extensively investigated modes of catalysis for forming CC bonds from CH bonds: PdII/Pd0, PdII/PdIV, Pd0/PdII/PdIV, and Pd0/PdII catalysis. A more detailed discussion is then directed towards the recent development of palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle. Despite the progress made to date, improving the versatility and practicality of this new reaction remains a tremendous challenge.

The heck reaction as a sharpening stone of palladium catalysis.

Abstract: s, or keywords if they used Heck-type chemistry in their syntheses, because it became one of basic tools of organic preparations, a natural way to

Aryl-aryl bond formation by transition-metal-catalyzed direct arylation.

Abstract: The biaryl structural motif is a predominant feature in many pharmaceutically relevant and biologically active compounds. As a result, for over a century 1 organic chemists have sought to develop new and more efficient aryl -aryl bond-forming methods. Although there exist a variety of routes for the construction of aryl -aryl bonds, arguably the most common method is through the use of transition-metalmediated reactions. 2-4 While earlier reports focused on the use of stoichiometric quantities of a transition metal to carry out the desired transformation, modern methods of transitionmetal-catalyzed aryl -aryl coupling have focused on the development of high-yielding reactions achieved with excellent selectivity and high functional group tolerance under mild reaction conditions. Typically, these reactions involve either the coupling of an aryl halide or pseudohalide with an organometallic reagent (Scheme 1), or the homocoupling of two aryl halides or two organometallic reagents. Although a number of improvements have developed the former process into an industrially very useful and attractive method for the construction of aryl -aryl bonds, the need still exists for more efficient routes whereby the same outcome is accomplished, but with reduced waste and in fewer steps. In particular, the obligation to use coupling partners that are both activated is wasteful since it necessitates the installation and then subsequent disposal of stoichiometric activating agents. Furthermore, preparation of preactivated aryl substrates often requires several steps, which in itself can be a time-consuming and economically inefficient process.