Colouring matters of Australian plants. XXIV. Haemofluorone B : New synthetic models and a revised structure

1981 ◽  
Vol 34 (3) ◽  
pp. 587 ◽  
Author(s):  
AL Chaffee ◽  
RG Cooke ◽  
IJ Dagley ◽  
P Perlmutter ◽  
RL Thomas
Keyword(s):  
Grignard Reagents ◽  
Trimethyl Ether ◽  
Synthetic Models

The occurrence of haemofluorone B in Anigozanthos rufus and Conostylis setosa has been confirmed. The revised structure 5,8,9-trihydroxy-3H-naphtho[2,1,8-mna]xanthen-3-one is now proposed for this pigment. Dihydroxyanigorufone has also been found in Conostylis setosa and the structure 9-(3,4-dihydroxyphenyl)-2-hydroxy-lH-phenalen-l-one has been confirmed by synthesis of the trimethyl ether. Some model arylphenalenones and naphthoxanthenones have been prepared fromnaphthylphenylpropanones and some unusual products have been obtained by photolysis of arylphenalenonesand by the reactions of Grignard reagents with phenalenones.

Fe-Catalyzed Conjunctive Cross-Couplings of Unactivated Alkenes with Grignard Reagents

2020 ◽  
Author(s):  
Lei Liu ◽  
Wes Lee ◽  
Cassandra R. Youshaw ◽  
Mingbin Yuan ◽  
Michael B. Geherty ◽  
...  
Keyword(s):  
Functional Groups ◽  
Cross Coupling ◽  
Alkyl Halides ◽  
Grignard Reagents ◽  
Turnover Frequency ◽  
Diverse Range ◽  
Cascade Cyclization ◽  
Radical Cascade

The first iron-catalyzed three-component cross-coupling of unactivated olefins with alkyl halides and Grignard reagents is reported. The reaction operates under fast turnover frequency and tolerates a diverse range of sp2-hybridized nucleophiles, alkyl halides, and unactivated olefins bearing diverse functional groups to yield the desired 1,2-alkylarylated products with high regiocontrol. Further, we demonstrate that this protocol is amenable for the synthesis of new (hetero)carbocycles including tetrahydrofurans and pyrrolidines via a three-component radical cascade cyclization/arylation that forges three new C-C bonds.

Structure Revision of Protoaculeine B, a Posttranslationally Modified N-Terminal Residue in the Peptide Toxin Aculeine B

2020 ◽  
Author(s):  
Raku Irie ◽  
Kei Miyako ◽  
Satoko Matsunaga ◽  
Ryuichi Sakai ◽  
Masato Oikawa
Keyword(s):  
Mass Spectra ◽  
Chemical Reactivity ◽  
Model Compounds ◽  
Structural Revision ◽  
Structure Revision ◽  
Peptide Toxin ◽  
One Step ◽  
Marine Peptide ◽  
Synthetic Models ◽  
Long Chain

<div>Here, we newly propose the structure of protoaculeine B, an N-terminal moiety of the marine peptide toxin aculeine B, as possessing the cis-disubstituted tetrahydro-beta-carboline framework. We prepared two truncated model compounds that lack long-chain polyamine by one-step Pictet-Spengler reaction of tryptophan, and compared the NMR and mass spectra and chemical reactivity with those of natural protoaculeine B. The synthetic models reproduced the profiles of the natural product well, which was conclusive for the structural revision.</div>

Design and Development of Fe-Catalyzed Intra- and Intermolecular Carbofunctionalization of Vinyl Cyclopropanes

2019 ◽  
Author(s):  
Lei Liu ◽  
Wes Lee ◽  
Mingbin Yuan ◽  
Chris Acha ◽  
Michael B. Geherty ◽  
...  
Keyword(s):  
Bond Formation ◽  
Cross Coupling ◽  
Alkyl Halides ◽  
Grignard Reagents ◽  
Mechanistic Studies ◽  
Radical Intermediates ◽  
Design And Implementation ◽  
Solvent Cage ◽  
Radical Cascade ◽  
Radical Processes

Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of the alkyl radical intermediates out of the solvent cage to participate in an intra- or -intermolecular radical cascade with the VCP followed by re-entering the Fe radical cross-coupling cycle to undergo selective C(sp2)-C(sp3) bond formation. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations.

Alkyl 1-[2-(oxido anion)-, 3-, 4-, 5-alkyl substituted]phenyl ketyl radicals

1979 ◽  
Vol 44 (6) ◽  
pp. 1731-1741 ◽  
Author(s):  
Andrej Staško ◽  
Ľubomír Malík ◽  
Alexander Tkáč ◽  
Vladimír Adamčík ◽  
Eva Maťašová
Keyword(s):  
Electron Donor ◽  
Unpaired Electron ◽  
Grignard Reagents ◽  
Slight Effect ◽  
Benzene Nucleus ◽  
Alkyl Groups ◽  
Splitting Constant

Reactions of R2,R3-alkyl substituted 2-hydroxybenzenecarboxylic acids 2-HO-C6H2R2-COOH with Grignard reagents R1MgBr in the presence of nickel give stable aryl alkyl ketyl radicals 2-O--R2-, R3-C6H2-CO--R1 where R1 = CH3, C2H5, C2D5, n-C3H7 and R2,R3 = CH3, C2H5, i-C3H7, t-C4H9. The β protons of ketyl group are equivalent (splitting constant 1.25 mT) and non-equivalent (splitting constants within 0.5 to 1.5 mT) for R1 = methyl and other alkyl groups, respectively. Interaction of the γ protons with the unpaired electron was only observed in the case of R1 = n-propyl (splitting constants about 0.07 mT). The substituents R1 have but slight effect on values of splitting constants of the protons in R2,R3 and vice versa. Also splitting constants of the benzene nucleus (a4H = 0.55 mT, a6H = 0.44 mT) are only slightly affected by the substituents R1,R2,R3, which indicates dominant electron-donor effect of the oxido-anion group eliminating the relatively smaller contributions of the alkyl substituents.

scholarly journals Joint analysis of the magnetic field and Total Gradient Intensity in Central Europe

2019 ◽  
Author(s):  
Maurizio Milano ◽  
Maurizio Fedi ◽  
J. Derek Fairhead
Keyword(s):  
Magnetic Field ◽  
Central Europe ◽  
Joint Analysis ◽  
East European ◽  
Long Wavelength ◽  
Low Degree ◽  
Total Gradient ◽  
Synthetic Models ◽  
The Magnetic Field ◽  
Different Altitudes

Abstract. In the European region, the magnetic field at satellite altitudes (~ 350 km) is mainly defined by a long-wavelength magnetic-low called here the Central Europe Magnetic Low (CEML), located to the southwest of the Trans European Suture Zone (TESZ). We studied this area by a joint analysis of the magnetic and total gradient (∇T) anomaly maps, for a range of different altitudes of 5 km, 100 km and 350 km. Tests on synthetic models showed the usefulness of the joint analysis at various altitudes to identify reverse dipolar anomalies and to characterize areas in which magnetization is weak. By this way we identified areas where either reversely or normally magnetized sources are locally dominant. At a European scale these anomalies are sparse, with a low degree of coalescence effect. The ∇T map indeed presents generally small values within the CEML area, indicating that the Palaeozoic Platform is weakly magnetized. At 350 km altitude, the TESZ effect is largely dominant: with intense ∇T highs above the East European Craton (EEC) and very small values above the Palaeozoic Platform, this again denoting a weakly magnetized crust. Small coalescence effects are masked by the trend of the TESZ. Although we identified sparsely located reversely magnetized sources in the Palaeozoic Platform of the CEML, the joint analysis does not support a model of a generally reversely magnetized crust. Instead, our analysis strongly favors the hypothesis that the CEML anomaly is mainly caused by a sharp contrast between the magnetic properties of EEC and Palaeozoic Platform.

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