Dearomatization Strategy Research Articles

Dearomatization Strategy and Palladium-Catalyzed Domino Reaction: Construction of Azepino[5,4,3-cd]indoles from 2-Alkynylanilines

A facile approach to construct 3,4-fused tricyclic azepino[5,4,3-cd]indoles from 2-alkynyl anilines, isocyanides, and α,β-unsaturated acids is reported. This synthetic process involves a regioselective meta-functionalization of 2-alkynylanilines using a dearomatization strategy and a palladium(II)-catalyzed domino heterocyclization/Heck reaction.

Imino exchange reaction in a dearomatization strategy: synthesis of N-acyl diarylamines and phenothiazines from two anilines

A dearomatization strategy of anilines involving an imino exchange as the key step was developed to prepare N-acyl-diarylamines and phenothiazines.

ChemInform Abstract: Dearomatization Strategy of β‐Enamino Ester: Construction of Indenoazepines via Tandem Michael Addition/Polycyclization.

A dearomatization strategy of β-enamino esters was developed to construct indenoazepine derivatives. The oxidative dearomatization was combined with a base-promoted tandem Michael addition/polycyclization and an acid-catalyzed aromatization. The nonaromatic structure of the Michael adducts might be essential to the realization of the 7-endo-dig cyclization.

Regio- and Enantiospecific Rhodium-Catalyzed Allylic Substitution with an Acyl Anion Equivalent

The construction of enantiomerically enriched acyclic quaternary substituted ketones via the regio- and enantiospecific rhodium-catalyzed allylic alkylation reaction of chiral nonracemic tertiary alcohols with cyanohydrin pronucleophiles is described. This approach provides an alternative method to the α-arylation and vinylation of acyclic disubstituted ketone enolates, which remains a challenging endeavor. The combination of the allylic alkylation with ring-closing metathesis facilitates the preparation of enantiomerically enriched 2,2-disubstituted naphthalene-1-ones, which have proven very difficult to prepare using a more conventional dearomatization strategy.

ChemInform Abstract: Model Studies Towards the Challenging Angularly‐Oxygenated Core of Several Angucyclinones from an Oxidative Dearomatization Strategy.

AbstractOxone‐mediated oxidative dearomatization of tricyclic phenol (IV) yields p‐quinol (VI), which is converted into azicemycin‐type tricyclic model (VI) and aquayamycin‐type core model (X).

Dearomatization Strategy of β-Enamino Ester: Construction of Indenoazepines via Tandem Michael Addition/Polycyclization

A dearomatization strategy of β-enamino esters was developed to construct indenoazepine derivatives. The oxidative dearomatization was combined with a base-promoted tandem Michael addition/polycyclization and an acid-catalyzed aromatization. The nonaromatic structure of the Michael adducts might be essential to the realization of the 7-endo-dig cyclization.

Model studies towards the challenging angularly-oxygenated core of several angucyclinones from an oxidative dearomatization strategy

Up to six differently substituted highly challenging angularly-oxygenated tricyclic core models of natural angucyclinones were stereoselectively synthesized from a common p-quinol intermediate obtained from Oxone-mediated oxidative dearomatization of the corresponding tricyclic phenol.

Recent Advances in Phenol Dearomatization and Its Application in Complex Syntheses

As a powerful tool, the dearomatization of phenols has been explored extensively and utilized by organic chemists during the course of complex syntheses. This review highlights recent advances in phenol dearomatizations, especially those accomplished in an enantioselective manner, and the application of dearomatization strategies in complex syntheses. 1 Introduction 2 New Developments in Phenol Dearomatization 3 Enantioselective Phenol Dearomatization 3.1 Controlled by Chiral Substrate 3.2 Controlled by Chiral Catalyst 3.3 Controlled by Chiral Hypervalent Iodine 4 Enantioselective Phenol Dearomatization Strategies in Complex Syntheses 4.1 With the Formation of a Carbon–Oxygen Bond 4.2 With the Formation of a Carbon–Carbon Bond 4.3 With the Formation of a Carbon–Nitrogen Bond 5 Conclusion

ChemInform Abstract: Divergent Construction of Nitrogen‐Containing Polycyclic Compounds with a Dearomatization Strategy.

AbstractThe dearomatization of p‐substituted ortho‐alkynyl anilines gives rise to a cyclohexadienimine intermediate of type (II).

ChemInform Abstract: Application of Dearomatization Strategy on the Synthesis of Furoquinolinone and Angelicin Derivatives.

AbstractThe novel approach is based on a cyclization/addition/aromatization/lactamization sequence.

Divergent Construction of Nitrogen-Containing Polycyclic Compounds with a Dearomatization Strategy

The oxidative dearomatization of para-substituted o-alkynylanilines afforded 2-alkynyl cyclohexadienimines, which can act as active substrates for reaction with electron-rich styrenes. The reaction is metal-controlled. Bi(OTf)3-catalyzed reactions afforded 3,4-dihydro-cyclopenta[c,d]indoles, and AgOTf-catalyzed reactions provided tricyclic pyrrole derivatives.

Application of Dearomatization Strategy on the Synthesis of Furoquinolinone and Angelicin Derivatives

The oxidative dearomatization of 3-(3-alkynyl-4-hydroxyphenyl)propanoic acid is combined with a cascade transition-metal catalyzed cyclization/addition/aromatization/lactamization sequence, which provides a novel approach to prepare furoquinolinone and angelicin derivatives in a convergent and efficient manner.

ChemInform Abstract: Nucleophilic Dearomatization of Chloromethyl Naphthalene Derivatives via η3‐Benzylpalladium Intermediates: A New Strategy for Catalytic Dearomatization.

AbstractA variety of chloroarylmethyl naphthalene derivatives undergoes dearomatization in the reaction with diethylmalonate (II) and analogues (IV).

Nucleophilic Dearomatization of Chloromethyl Naphthalene Derivatives via η3-Benzylpalladium Intermediates: A New Strategy for Catalytic Dearomatization

Palladium-catalyzed nucleophilic dearomatization of chloromethyl naphthalene derivatives to produce ortho- or para-substituted carbocycles in satisfactory to excellent yields has been developed. The unprecedented dearomatization reactions proceeded smoothly under mild conditions via η(3)-benzylpalladium intermediates.

Dearomatization strategies in the synthesis of complex natural products.

Evolution in the field of the total synthesis of natural products has led to exciting developments over the last decade. Numerous chemoselective and enantioselective methodologies have emerged from total syntheses, resulting in efficient access to many important natural product targets. This Review highlights recent developments concerning dearomatization, a powerful strategy for the total synthesis of architecturally complex natural products wherein planar, aromatic scaffolds are converted to three-dimensional molecular architectures.

An Enantioselective Organocatalytic Oxidative Dearomatization Strategy

We have developed a catalytic enantioselective strategy for chemical synthesis wherein flat aromatic molecules are directly converted to complex nonracemic molecular architectures. The process involves oxidative dearomatization of substituted phenols followed by a desymmetrizing secondary amine-catalyzed asymmetric intramolecular Michael addition and reveals a decalin structure, formed with exquisite control of three new stereogenic centers and an array of exploitable orthogonal functionality, directly from a flat molecule that is devoid of architectural complexity.