Atroposelective Access to Dihydropyridinones with C–N Axial and Point Chirality via NHC-Catalyzed [3 + 3] Annulation

Li, Yanting; Duan, Xiaoyong; Yang, Chengxian; Wei, Yamei; Li, Jiahan; Ren, Xiaojie; Qi, Jing

doi:10.1021/acs.joc.3c00854

“… [46] Mechanistically, this reaction proceeded through the formation of cyclic bis‐hemiaminal N , followed by sequential dehydration and tautomerization, wherein the tautomerization of O to 77 was the key enantiodetermining step. Very recently, Duan, Qi, and co‐workers achieved the synthesis of axially chiral dihydropyridones bearing a central chirality through an NHC‐catalyzed atroposelective (3+3) annulation of enals with 2‐aminomaleate derivatives [47] …”

Section: Atropisomers With C‐stereogenic Centersmentioning

confidence: 99%

“…Very recently, Duan, Qi, and co-workers achieved the synthesis of axially chiral dihydropyridones bearing a central chirality through an NHC-catalyzed atroposelective (3 + 3) annulation of enals with 2-aminomaleate derivatives. [47]…”

Section: Other Catalytic Atroposelective Approachesmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Zhang,

Li,

Liu

et al. 2023

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With the rapid development of asymmetric catalysis, the demand for the enantioselective synthesis of complex and diverse molecules with different chiral elements is increasing. Owing to the unique features of atropisomerism, the catalytic asymmetric synthesis of atropisomers has attracted a considerable interest from the chemical science community. In particular, introducing additional chiral elements, such as carbon center chirality, heteroatomic chirality, planar chirality, and helical chirality, into atropisomers provides an opportunity to incorporate new properties into axially chiral compounds, thus expanding the potential applications of atropisomers. Thus, it is important to perform catalytic asymmetric transformations to synthesize atropisomers bearing multiple chiral elements. In spite of challenges in such transformations, in recent years, chemists have devised powerful strategies under asymmetric organocatalysis or metal catalysis, synthesizing a wide range of enantioenriched atropisomers bearing multiple chiral elements. Therefore, the catalytic asymmetric synthesis of atropisomers bearing multiple chiral elements has become an emerging field. This minireview summarizes the rapid progress in this field and indicates challenges, thereby promoting this field to a new horizon.

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“…Various NHC-catalyzed techniques including atroposelective annulation, resolution/desymmetrization, and central to axial chirality transfer have been showcased to generate a variety of biaryls and related compounds having a C–C chiral axis. Furthermore, molecules containing a chiral C–N axis can also be synthesized utilizing NHC catalysis . Despite the application of NHC catalysis in generating C–C and C–N atropoisomers, the preparation of more challenging N–N atropoisomers employing NHC-organocatalysis has received scant attention.…”

Section: Introductionmentioning

confidence: 99%

Atroposelective Synthesis of N–N Axially Chiral Indoles and Pyrroles via NHC-Catalyzed Diastereoselective (3 + 3) Annulation Strategy

Ranganathappa,

Dehury,

Singh

et al. 2024

ACS Catal.

4

0

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The synthesis of N−N axially chiral molecules in the enantiopure form has emerged as an interesting research topic primarily due to the significance and intricacy in synthesizing these molecules, especially bearing heterocyclic motifs. Herein, we disclose a method for the introduction of N−N axial chirality along with a point chiral center via the N-heterocyclic carbene (NHC)catalyzed atroposelective synthesis of dihydropyridinone-containing indoles and pyrroles. The reaction follows a (3 + 3) annulation approach by the interception of indole/pyrrole-derived enamines with α,β-unsaturated aldehydes under oxidative NHC catalysis proceeding via the α,β-unsaturated acylazoliums. The N−N axially chiral indoles/pyrroles were formed under mild conditions in broad scope with high selectivity. In addition, preliminary DFT studies of the N−N rotational barrier of the axially chiral products were performed.

show abstract

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Zhang,

Li,

Liu

et al. 2023

View full text Add to dashboard Cite

With the rapid development of asymmetric catalysis, the demand for the enantioselective synthesis of complex and diverse molecules with different chiral elements is increasing. Owing to the unique features of atropisomerism, the catalytic asymmetric synthesis of atropisomers has attracted a considerable interest from the chemical science community. In particular, introducing additional chiral elements, such as carbon center chirality, heteroatomic chirality, planar chirality, and helical chirality, into atropisomers provides an opportunity to incorporate new properties into axially chiral compounds, thus expanding the potential applications of atropisomers. Thus, it is important to perform catalytic asymmetric transformations to synthesize atropisomers bearing multiple chiral elements. In spite of challenges in such transformations, in recent years, chemists have devised powerful strategies under asymmetric organocatalysis or metal catalysis, synthesizing a wide range of enantioenriched atropisomers bearing multiple chiral elements. Therefore, the catalytic asymmetric synthesis of atropisomers bearing multiple chiral elements has become an emerging field. This minireview summarizes the rapid progress in this field and indicates challenges, thereby promoting this field to a new horizon.

show abstract

Atroposelective Access to Dihydropyridinones with C–N Axial and Point Chirality via NHC-Catalyzed [3 + 3] Annulation

Cited by 5 publications

References 65 publications

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

Atroposelective Synthesis of N–N Axially Chiral Indoles and Pyrroles via NHC-Catalyzed Diastereoselective (3 + 3) Annulation Strategy

Catalytic Asymmetric Synthesis of Atropisomers Bearing Multiple Chiral Elements: An Emerging Field

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