Total Synthesis of Chaetoglobin A via Catalytic, Atroposelective Oxidative Phenol Coupling.

@article{Kang2018TotalSO,
  title={Total Synthesis of Chaetoglobin A via Catalytic, Atroposelective Oxidative Phenol Coupling.},
  author={Houng Kang and Carilyn Torruellas and Jinchu Liu and Marisa C. Kozlowski},
  journal={Organic letters},
  year={2018},
  volume={20 18},
  pages={
          5554-5558
        }
}
The first total synthesis of chaetoglobin A (1), which features a chiral axis between two identical highly oxygenated bicyclic cores, was successfully completed in 12 steps from 2,6-dimethoxytoluene. Vanadium-catalyzed oxidative phenol coupling, as a key step, enabled generation of the axial chirality. 

Figures from this paper

Chiral Dinuclear Vanadium Complex-Mediated Oxidative Coupling of Resorcinols.

A method for the highly regio- and enantioselective oxidative coupling of resorcinols has been established by using dibrominated dinuclear vanadium(V) catalyst 1c under air. When resorcinols bearing

Total Synthesis of Pyrolaside B: PhenolTrimerization via Sequenced Oxidative C-C and C-O Coupling.

The key strategy used for this novel synthesis is the facile one-step construction of a spiroketal trimer intermediate which can be selectively reduced to give the natural product framework without recourse to stepwise Ullmann- and Suzuki-type couplings.

Chemo- and enantioselective hetero-coupling of hydroxycarbazoles catalyzed by a chiral vanadium(v) complex

The catalytic enantioselective oxidative hetero-coupling of arenols using a chiral vanadium(v) complex has been developed.

Synthetic Applications of Oxidative Aromatic Coupling—From Biphenols to Nanographenes

Analysis of the progress achieved in this field since 2013 reveals that many groups have contributed by pushing the boundary of structural possibilities, expanding into surface‐assisted (cyclo)dehydrogenation, and developing new reagents.

Phenol-Directed C–H Functionalization

Phenols are important starting materials, intermediates, and functional elements of a very broad range of chemicals and materials. They are large-volume products of benzene oxidation and are

Catalytic Oxidative Coupling of Phenols and Related Compounds.

Phenols and their derivatives are the elementary building blocks for several classes of complex molecules that play essential roles in biological systems. Nature has devised methods to selectively

Recent advances in the chemistry and biology of azaphilones

A total of 252 compounds predominantly originated from 32 genera of fungi, such as Penicillium and Talaromyces, were included in this research, of which over 40% displayed cytotoxic/anti-tumor effects.

Stereodivergent, Chemoenzymatic Synthesis of Azaphilone Natural Products.

An approach for accessing biocatalysts with complementary selectivity that is orthogonal to protein engineering is reported, and the first syntheses of trichoflectin, deflectin-1a, and lunatoic acid A were achieved.

References

SHOWING 1-10 OF 69 REFERENCES

Asymmetric Oxidative Coupling of Phenols and Hydroxycarbazoles

Generation of a more vanadium catalyst by ligand design and by addition of an exogenous Brønsted or Lewis acid was found to be key to coupling the more oxidatively resistant phenols.

Total synthesis of (+)-brefeldin A.

(+)-Brefeldin A was synthesized through an efficient route, which features (1) construction of the five-membered ring from a Crimmins aldol via tandem Li-I exchange and carbanion-mediated cyclization

One-pot synthesis of highly substituted 4-acetonylindoles via sequential dearomatization and silver-catalyzed domino reaction.

Synthetically useful 4-acetonylindoles have been conveniently prepared from 2-alkynylanilines and silyl enol ethers using a dearomatization strategy using a two-step/one-pot protocol and a silver-catalyzed domino reaction.

Total synthesis of (+/-)-mitorubrinic acid.

Mitorubrinic acid, a member of the azaphilone family of natural products, has been constructed in 12 steps by elaboration and oxidative dearomatization of an isocoumarin intermediate to provide the azphilone nucleus with a disubstituted, unsaturated carboxylic acid side chain.

Asymmetric syntheses of (-)-mitorubrin and related azaphilone natural products.

Asymmetric syntheses of (-)-mitorubrin and related azaphilone natural products are reported. Key steps involve copper-mediated, enantioselective oxidative dearomatization to prepare the azaphilone

Synthesis of azaphilone-based chemical libraries.

The synthesis of azaphilone scaffolds that have been further diversified by cross coupling acylation and amine addition is reported, including vinylogous pyridones which project diversity elements in four sectors of the azphilone core.

Sterically controlled iodination of arenes via iridium-catalyzed C-H borylation.

The iodination of boronic esters has potential for the synthesis of radiolabeled aryl iodides, as demonstrated by the concise synthesis of a potential tracer for SPECT imaging.
...