Chirality Transfer Intramolecular Pauson–Khand Reaction with N–C Axially Chiral Sulfonamides Bearing an Ene–Yne Structure

Kasahara, Ryohei; Toyoda, Tatsuya; Fukasawa, Sota; Takeuchi, Aoi; Sato, Azusa; Hori, Akiko; Kitagawa, Osamu

doi:10.1021/acs.orglett.3c02893

Cited by 2 publications

(2 citation statements)

References 43 publications

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“…We have explored C–N axially chiral chemistry for over 25 years, and reported the first catalytic asymmetric synthesis of C–N axially chiral compounds ( N -allylated ortho - tert -butylanilides IA ) in 2002 . However, the enantioselectivity of this method using chiral Pd-catalyzed N -allylation (Tsuji–Trost allylation) was by no means satisfactory (35–44% ee).…”

Section: Introductionmentioning

confidence: 99%

Structural Chemistry of C–N Axially Chiral Compounds

Kitagawa

2024

J. Org. Chem.

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In the last several years, atropisomers owing to the rotational restriction around a C−N single bond (C−N axially chiral compounds) have attracted significant attention in the field of synthetic organic chemistry. In particular, the highly enantioselective synthesis of various C− N axially chiral compounds and their application to asymmetric reactions have been reported by many groups. On the other hand, studies on the structural chemistry of C−N axially chiral compounds have attracted scant attention in comparison with synthetic studies. For over 25 years, our group has explored asymmetric synthesis of C−N axially chiral compounds and their synthetic application. In the course of these synthetic studies, we found several notable structural properties in relation to the C−N bond rotation and an association of enantiomers (the relationship between the rotational stability and the structure or electronic effect, the chiralitydependent halogen bond, and the self-disproportionation of enantiomers). Furthermore, on the basis of these structural properties, the development of acid-mediated molecular rotors and the synthesis of isotopic atropisomers possessing high stereochemical purity and rotational stability were achieved. Through this Perspective, I wish to make the chemistry community aware that C−N axially chiral compounds are attractive molecules from the viewpoints of both synthetic organic chemistry and structural chemistry.

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Section: Introductionmentioning

confidence: 99%

Structural Chemistry of C–N Axially Chiral Compounds

Kitagawa

2024

J. Org. Chem.

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“…Most N–C axially chiral compounds, which were prepared through a catalytic asymmetric method, are either carboxamide derivatives or nitrogen-containing aromatic heterocycles. Furthermore, N–C axially chiral carboxamide products have been widely used in asymmetric reactions as chiral building blocks. , For example, the reaction of cinnamyl bromide with the enolate prepared from enantioenriched o-tert -butylanilide I gave α-cinnamylation product II (S N 2 product) with high diastereoselectivity (Scheme A)…”

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confidence: 99%

Regio- and Stereoselective α-Allylation with Enolates Prepared from N–C Axially Chiral Thiolactam and Lactam

Sakagami,

Matsui,

Aoyama

et al. 2024

J. Org. Chem.

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The reaction of allyl bromide derivatives with the enolate prepared from enantioenriched N−C axially chiral N-(2,5di-tert-butylphenyl)-3,4-dihydroquinolin-2-one (lactam) and -thione (thiolactam) proceeded in a completely regio-and stereoselective manner to afford S N 2 and S N 2′-like products, respectively. Furthermore, through the conversion of thiolactam to lactam, the regiodivergent and stereoselective synthesis of N−C axially chiral lactams bearing a chiral tertiary α-carbon was achieved.

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Chirality Transfer Intramolecular Pauson–Khand Reaction with N–C Axially Chiral Sulfonamides Bearing an Ene–Yne Structure

Cited by 2 publications

References 43 publications

Structural Chemistry of C–N Axially Chiral Compounds

Structural Chemistry of C–N Axially Chiral Compounds

Regio- and Stereoselective α-Allylation with Enolates Prepared from N–C Axially Chiral Thiolactam and Lactam

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