Substituent

Summary

In organic chemistry, a substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule. (in organic chemistry and biochemistry, the terms substituent and functional group, as well as side chain and pendant group, are used almost interchangeably to describe those branches from the parent structure, though certain distinctions are made in polymer chemistry. In polymers, side chains extend from the backbone structure. In proteins, side chains are attached to the alpha carbon atoms of the amino acid backbone.) The suffix -yl is used when naming organic compounds that contain a single bond replacing one hydrogen; -ylidene and -ylidyne are used with double bonds and triple bonds, respectively. In addition, when naming hydrocarbons that contain a substituent, positional numbers are used to indicate which carbon atom the substituent attaches to when such information is needed to distinguish between isomers. Substituents c

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Directed Biosynthesis of Phytotoxic Alkaloids in the Cyanobacterium Nostoc 78-12A

Karl Gademann, Theresa Myers, Cyril Portmann, Cora Prestinari

Nostocarboline, a chlorinated and N-methylated carbolinium alkaloid, displays potent and selective inhibition of photoautotrophic organisms as well as the malaria parasite Plasmodium falciparum, while showing very low toxicity to bacterial and fungal pathogens, rat myoblasts and crustaceans. New derivatives of nostocarboline incorporating Br, F or methyl substituents have been obtained through precursor-directed biosynthesis in Nostoc 78-12A (identical to Nostoc sp. ATCC 43238) by feeding this cyanobacterium with differently substituted tryptophan derivatives or 6-Br-norharmane (eudistomin N). These experiments substantiate the biosynthetic hypothesis and validate the inherent flexibility of the corresponding enzymes for metabolic engineering. The new derivatives inhibit the growth of the toxic-bloom-forming cyanobacterium Microcystis aeruginosa PCC 7806 above 1 μM. The mode of action of nostocarboline was investigated by using chlorophyll-a fluorescence imaging, and it was demonstrated that a decrease in photosynthesis precedes cell death, thus establishing the phytotoxic properties of this alkaloid.

2009

The development of a sequential copper-catalyzed oxy-alkynylation/intramolecular [4+2] cycloaddition of allenes and arenes was investigated at first. This one-pot protocol allowed the construction of complex polycylic architectures with high efficiency from aryldiazo esters and ethynylbenziodoxolone reagents (EBX). The mild reaction conditions (23 to 90 Â°C) for the dearomatization step was unusual compared to previous literature reports and DFT computations showed that substituents on the aryl ring resulted in favorable dispersive interactions, decreasing the activation energy barrier of the cycloaddition. The bicyclo[2.2.2]octadiene products were successfully applied as ligands for rhodium. The prepared diene-rhodium complexes were extensively characterized by NMR spectroscopy and X-ray crystallography. Finally, an enantiopure ligand having a pseudo C2-symmetry was used in the conjugate addition of phenylboronic acid to cyclohexenone and furnished the Î²-functionalized ketone in good yield and with high enantioselectivity.The vinylation reactions of diazo compounds are scarce. A successful copper-catalyzed vinylation of diazo compounds with vinylbenziodoxolone reagents (VBX) as partners was reported. The transformation allowed an unprecedented gem-oxy-vinylation at the carbene center, providing functionalized Î±-vinyl-hydroxyacid derivatives in high atom and step economy. The products were obtained in excellent yields and contained synthetically versatile functional groups for post-modifications. The development of an enantioselective version of this reaction was limited and further investigations will be required to obtain high enantioselectivities. In addition, a practical synthesis of alkyl-substituted VBX reagents has been established; VBX reagents being limited to aryl substituents until then. Multicomponent reactions provide efficient means to rapidly access molecular diversity. A copper(I)-catalyzed threeâcomponent reaction utilizing diazo compounds, alcohols as nucleophiles and vinyl- or ethynylbenziodoxole reagents, was successfully developed. The transformation allowed the synthesis of highly functionalized allyl and propargyl ethers. The scope is broad, and extensive variations of the three partners of the reaction is possible, leading to maximal structural diversity. Extension of this work to N-nucleophiles was not as straightforward as anticipated, but good results could be obtained with anilines, trifluorodiazoethane and EBX reagents as components.Questions about the reaction mechanisms of the copper-catalyzed difunctionalizations of diazo compounds with VBX and EBX reagents have been frequent all-along this research work. Preliminary results of in-depth mechanistic investigations have been obtained. The initial assumption of an internal alkyne transfer step was first invalidated by DFT computations and was latter refuted experimentally. A complexation between the carboxylate of ethynylbenziodoxolone reagents and the copper catalyst was characterized by NMR spectroscopy and contrasted to a alkyne-copper interaction observed with ethynylbenziodoxole reagents. These two possible complexes were supported by DFT calculations. Finally, non-classical sigmoidal kinetic profiles of the oxy-alkynylation reaction were obtained by in situ 19F NMR monitoring and the Cu-EBX complex is presumably involved in the observed induction periods.

EPFL2021

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Chiral alkyl amines are omnipresent as bioactive molecules and synthetic intermediates. The catalytic and enantioselective synthesis of alkyl amines from readily accessible precursors is challenging. Here we develop a nickel-catalyzed hydroalkylation method to assemble a wide range of chiral alkyl amines from enecarbamates (N-Cbz-protected enamines) and alkyl halides with high regio- and enantioselectivity. The method works for both nonactivated and activated alkyl halides and is able to produce enantiomerically enriched amines with two minimally differentiated alpha-alkyl substituents. The mild conditions lead to high functional group tolerance, which is demonstrated in the postproduct functionalization of many natural products and drug molecules, as well as the synthesis of chiral building blocks and key intermediates to bioactive compounds.

AMER CHEMICAL SOC2021

EPFL2021