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Dequirez G.,CNRS Natural Product Chemistry Institute | Pons V.,CNRS Natural Product Chemistry Institute | Dauban P.,CNRS Natural Product Chemistry Institute
Angewandte Chemie - International Edition | Year: 2012

The element nitrogen is essential to life. Considerable attention is thus paid to the development of synthetic methods for its introduction into molecules. Nitrenes, long regarded as highly reactive but poorly selective species, have recently emerged as useful tools for the formation of C-N bonds. Practical metal-catalyzed protocols are now available for the preparation of amines through either the aziridination of alkenes or the C-H amination of alkanes. Recent results highlighted in this Minireview suggest that synthetic nitrene chemistry is maturing with a wider scope not limited to these two reactions. Long regarded as highly reactive but poorly selective species, nitrenes have recently emerged as useful tools for C-N bond-forming reactions. Their capacity to insert into various bonds has led to the development of efficient catalytic C-H amination and alkene aziridination reactions. In recent work several click-type reactions using nitrenes have been developed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


Marinetti A.,CNRS Natural Product Chemistry Institute | Jullien H.,CNRS Natural Product Chemistry Institute | Voituriez A.,CNRS Natural Product Chemistry Institute
Chemical Society Reviews | Year: 2012

This review illustrates enantioselective transition-metal promoted skeletal rearrangements of polyunsaturated substrates possessing olefin, alkyne or allene functions. These processes are classified according to the number of carbon atoms involved in the cyclization, from (1C+1C) to (2C+2C+2C) or (2C+5C) cyclizations. Thus, for instance, (1C+1C) processes are typified notably by Alder-ene type reactions taking place mainly under palladium and rhodium catalysis, in the presence of chiral phosphorus ligands. Also, rhodium, platinum, and gold promoted insertions of unsaturated carbon-carbon bonds into C-H bonds belong to this class. For each class of reactions or substrate type the best ligand-metal pairs are highlighted. Unfortunately, unlike other transition metal promoted reactions, the mechanisms of chiral induction and stereochemical pathways have not been established so far in any of these reactions. In only a few instances, qualitative heuristic models have been tentatively proposed. Although the available stereochemical information is systematically given here, the paper focuses mainly on synthetic aspects of enantioselective cycloisomerizations. © 2012 The Royal Society of Chemistry.


Crich D.,CNRS Natural Product Chemistry Institute
Accounts of Chemical Research | Year: 2010

Glycosylation is arguably the most important reaction in the field of glycochemistry, yet it involves one of the most empirically interpreted mechanisms in the science of organic chemistry. The β-mannopyranosides, long considered one of the more difficult classes of glycosidic bond to prepare, were no exception to this rule. A number of logical but circuitous routes for their preparation were described in the literature, but they were accompanied by an even greater number of mostly ineffective recipes with which to access them directly. This situation changed in 1996 with the discovery of the 4,6-O-benzylidene acetal as a control element permitting direct entry into the β-mannopyranosides, typically with high yield and selectivity. The unexpected nature of this phenomenon demanded study of the mechanism, leading first to the demonstration of the α-mannopyranosyl triflates as reaction intermediates and then to the development of α-deuterium kinetic isotope effect methods to probe their transformation into the product glycosides. In this Account, we assemble our observations into a comprehensive assessment consistent with a single mechanistic scheme. The realization that in the glucopyranose series the 4,6-O-benzylidene acetal is α-rather than β-directing led to further investigations of substituent effects on the stereoselectivity of these glycosylation reactions, culminating in their explanation in terms of the covalent α-glycosyl triflates acting as a reservoir for a series of transient contact and solvent-separated ion pairs. The function of the benzylidene acetal, as explained by Bols and co-workers, is to lock the C6-O6 bond antiperiplanar to the C5-O5 bond, thereby maximizing its electron-withdrawing effect, destabilizing the glycosyl oxocarbenium ion, and shifting the equilibria as far as possible toward the covalent triflate. β-Selective reactions result from attack of the nucleophile on the transient contact ion pair in which the α-face of the oxocarbenium ion is shielded by the triflate counterion. The α-products arise from attack either on the solvent-separated ion pair or on a free oxocarbenium ion, according to the dictates of the anomeric effect. Changes in selectivity from varying stereochemistry (glucose versus mannose) or from using different protecting groups can be explained by the shifting position of the key equilibria and, in particular, by the energy differences between the covalent triflate and the ion pairs. Of particular note is the importance of substitutents at the 3-position of the donor; an explanation is proposed that invokes their evolving torsional interaction with the substituent at C2 as the chair form of the covalent triflate moves toward the half-chair of the oxocarbenium ion. © 2010 American Chemical Society.


Roulland E.,CNRS Natural Product Chemistry Institute
Angewandte Chemie - International Edition | Year: 2011

Meet the challenge! The time has come for organic chemists to devise more economically and ecologically sustainable strategies for multistep synthesis. One way to meet this challenge is to achieve protecting-group-free total synthesis. The recent progress accomplished in the field of catalyzed reactions will help chemists to meet this challenge (see figure; PG=protecting group). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


Masson G.,CNRS Natural Product Chemistry Institute | Lalli C.,CNRS Natural Product Chemistry Institute | Benohoud M.,CNRS Natural Product Chemistry Institute | Dagousset G.,CNRS Natural Product Chemistry Institute
Chemical Society Reviews | Year: 2013

The aza-Diels Alder reaction has become one of the most widely used synthetic tools for the preparation of N-containing 6-membered heterocycles. Numerous important developments have been reported to render this reaction catalytic and enantioselective. This tutorial review highlights strategies and recent advances to achieve high efficiency and selectivity through the use of organocatalysts and transition metal complexes, allowing also the extension of this transformation substrate scope. © 2013 The Royal Society of Chemistry.


Desnous C.,CNRS Natural Product Chemistry Institute | Guillaume D.,French National Center for Scientific Research | Clivio P.,French National Center for Scientific Research
Chemical Reviews | Year: 2010

The unique photoreactivity of spore DNA was studied. Since spore photoproduct formation under the influence of UV-A and B can be in part prevented by spore outer layer components, spore photoproduct formation under UV-C radiation and its subsequent efficient repair also raises the question of rationale for the conservation of this process in some Bacillus species and also of the preservation of some of its associated molecules. It can be easily understood that a UV-C protective system was necessary for prokaryote survival when it was reaching the Earth's surface. Even if under sunlight SP DNA is formed in small amounts in bacterial spore DNA, such wavelengths lead to other photoproducts whose biological importance appears also critical and consequently whose repair is highly important for spore survival. SPDNA formation and repair could be viewed as a complex but seldom used protective pathway whose genetic information has been preserved.


Collet F.,CNRS Natural Product Chemistry Institute | Lescot C.,CNRS Natural Product Chemistry Institute | Dauban P.,CNRS Natural Product Chemistry Institute
Chemical Society Reviews | Year: 2011

Catalytic C-H amination has recently emerged as a unique tool for the synthesis of amines. This tutorial review highlights the existing protocols catalyzed by metal complexes (rhodium, copper, ruthenium, manganese and palladium) allowing diastereo- and enantioselective C-H amination. Substrate-, catalyst- and reagent-controlled methodologies are detailed. They involve either catalytic nitrene C-H insertion or C-H activation. © 2011 The Royal Society of Chemistry.


Li J.,CNRS Natural Product Chemistry Institute | Neuville L.,CNRS Natural Product Chemistry Institute
Organic Letters | Year: 2013

An efficient copper-catalyzed synthesis of 1,2,4-trisubstituted imidazoles using amidines and terminal alkynes has been developed. Overall, the oxidative process, which involves Na2CO3, pyridine, a catalytic amount of CuCl2·2H2O, and oxygen (1 atm), consisted of a regioselective diamination of alkynes allowing the synthesis of diverse imidazoles in modest to good yields. © 2013 American Chemical Society.


Rodriguez R.,CNRS Natural Product Chemistry Institute | Rodriguez R.,University Pierre and Marie Curie | Miller K.M.,University of Texas at Austin
Nature Reviews Genetics | Year: 2014

Small molecules-including various approved and novel cancer therapeutics-can operate at the genomic level by targeting the DNA and protein components of chromatin. Emerging evidence suggests that functional interactions between small molecules and the genome are non-stochastic and are influenced by a dynamic interplay between DNA sequences and chromatin states. The establishment of genome-wide maps of small-molecule targets using unbiased methodologies can help to characterize and exploit drug responses. In this Review, we discuss how high-throughput sequencing strategies, such as ChIP-seq (chromatin immunoprecipitation followed by sequencing) and Chem-seq (chemical affinity capture and massively parallel DNA sequencing), are enabling the comprehensive identification of small-molecule target sites throughout the genome, thereby providing insights into unanticipated drug effects.


Courant T.,CNRS Natural Product Chemistry Institute | Masson G.,CNRS Natural Product Chemistry Institute
Chemistry - A European Journal | Year: 2012

Radical-polar crossover reaction: The photoredox-mediated alkylation of enamides with diethyl bromomalonate in the presence of alcohols has been developed. This multicomponent domino process affords β-alkylated α-carbamido ethers as stables imine surrogates in good to excellent yields under mild conditions (see scheme). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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