Recent Advances on the Construction of Chiral Dihydrobenzofurans by Asymmetric [3+2] Cyclization Reactions of Phenols (Quinones) and Alkenes DOI Open Access

Lai Zhang,

Jian Xiao, Ya‐Wen Wang

et al.

Acta Chimica Sinica, Journal Year: 2022, Volume and Issue: 80(8), P. 1152 - 1152

Published: Jan. 1, 2022

Dihydrobenzofuran structural units are widely present in bioactive natural products, and therefore, this type of products have attracted extensive attention from synthetic organic chemists pharmaceutical chemists.In recent years, enantioselective formation unit, especially its C2 C3 vicinal chiral stereocenters, has always been one challenging problems the field methodology.Among some methods, construction optically active dihydrobenzofuran [3＋2] cyclizations phenols (quinones) olefins via asymmetric catalysis or induction by auxiliaries developed rapidly.In review, we summarized progress cyclization reactions with different types catalysts auxiliaries, emphasis on understanding control stereoselectivies these methods.Meanwhile, application total synthesis dihydrobenzofurans enabled was briefly introduced.Finally, future development trend [3＋ 2] analyzed, order to stimulate emergence highly efficient general catalytic system.

Language: Английский

Regioselective Dearomative Amidoximation of Nonactivated Arenes Enabled by Photohomolytic Cleavage of N‐nitrosamides DOI
Pan‐Feng Yuan,

Xie‐Tian Huang,

Linhong Long

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(8)

Published: Jan. 5, 2024

Abstract Dearomative spirocyclization reactions represent a promising means to convert arenes into three‐dimensional architectures; however, controlling the regioselectivity of radical dearomatization with nonactivated afford spirocyclizative 1,2‐difunctionalization other than its kinetically preferred 1,4‐difunctionalization is exceptionally challenging. Here we disclose novel strategy for dearomative 1,2‐ or 1,4‐amidoximation (hetero)arenes enabled by direct visible‐light‐induced homolysis N−NO bonds nitrosamides, giving rise various highly regioselective amidoximated spirocycles that previously have been inaccessible required elaborate synthetic efforts. The mechanism and origins observed regioselectivities were investigated control experiments density functional theory calculations.

Language: Английский

Citations

6
Development of novel transition metal-catalyzed synthetic approaches for the synthesis of a dihydrobenzofuran nucleus: a review DOI Creative Commons

Rabia Ashraf,

Ameer Fawad Zahoor, Kulsoom Ghulam Ali

et al.

RSC Advances, Journal Year: 2024, Volume and Issue: 14(21), P. 14539 - 14581

Published: Jan. 1, 2024

The synthesis of dihydrobenzofuran scaffolds bears pivotal significance in the field medicinal chemistry and organic synthesis. These heterocyclic hold immense prospects owing to their significant pharmaceutical applications as they are extensively employed essential precursors for constructing complex frameworks. Their versatility importance make them an interesting subject study researchers scientific community. While exploring synthesis, have unveiled various novel efficient pathways assembling core. In wake extensive data being continuously reported each year, we outlined recent updates (post 2020) on methodological accomplishments employing catalytic role several transition metals forge functionalities.

Language: Английский

Citations

6
Coupling partner-dependent unsymmetrical C–H functionalization of N-phenoxyacetamides leading to sophisticated spirocyclic scaffolds DOI

Xia Song,

Kelin Wang,

Lian Xue

et al.

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(17), P. 4583 - 4590

Published: Jan. 1, 2022

In this paper, a coupling partner-dependent unsymmetrical C–H functionalization of N -phenoxyacetamides leading to the formation sophisticated spirocyclic scaffolds is presented.

Language: Английский

Citations

25
Expedient Access to Enantioenriched 1‐Azaspiro Cyclobutanones Enabled by Modified Heyns Rearrangement DOI

Shibaram Panda,

Prasanta Ghorai

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(32)

Published: June 13, 2023

Leveraging the unexplored regions of chemical space, integration spirocyclic cyclobutane in a molecular scaffold opens up new vista modern drug discovery. Despite recent advancements achieving synthesis such motifs, strategies for their asymmetric construction have not been well-recognized and remain formidable challenge. Herein, first time, we demonstrated chiral Brønsted acid-catalyzed enantioselective 1-azaspiro cyclobutanone enabled by an unusual reactivity enamine that explore potentiality Heyns rearrangement upon electrophilic modification. This design strategy offers viable access to wide range containing spiroindoline spiropyrrolidine derivatives good yields with excellent stereoselectivities (up >99 % ee, >20 : 1 dr). Furthermore, practicality this methodology has shown scale-up products facile post-synthetic modifications.

Language: Английский

Citations

14
Asymmetric Intramolecular Amination Catalyzed with Cp*Ir-SPDO via Nitrene Transfer for Synthesis of Spiro-Quaternary Indolinone DOI
Shiqiang Wei, Zihao Li, Shuanghu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18841 - 18847

Published: July 8, 2024

An asymmetric intramolecular spiro-amination to high steric hindering

Language: Английский

Citations

5
DBU-catalyzed annulation strategy for modular assembly of 2,3-difunctionalized dihydrobenzofurans DOI

Lili Yuan,

Jie Wang, Qiang Tang

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

An organocatalytic approach for the construction of 2,3-dihydrobenzofuran scaffold through a formal [4 + 1] annulation 2-(2-nitrovinyl)phenols and α-bromoacetophenones in presence 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) has been developed. This protocol could be easily performed one mmol scale, giving broad range derivatives moderate to excellent yields remarkable diastereoselectivity (>20 : 1 dr general) with good functional group tolerance.

Language: Английский

Citations

0
La(OTf)3-Catalyzed [3+2] Cycloaddition Reactions for the Synthesis of Benzo[d]oxazoles/Benzofurans DOI
Zhanjun Li, Yalin Zhang, Manman Sun

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(6), P. 3809 - 3820

Published: Feb. 23, 2024

The La(OTf)3-catalyzed [3+2] cycloaddition reactions for the synthesis of benzo[d]oxazoles/benzofurans via quinones and 1,2-di-tert-butyl-3-(cyanimino)diaziridine (1,3-di-tert-butyl-2-cyanoguanidine)/vinyl azides have been explored. A series 5-hydroxybenzofuran-4-carboxylic acid derivatives 5-hydroxybenzo[d]oxazole-4-carboxylic were conveniently obtained with high yields good stereoselectivities, which could be used further transformations to valuable compounds.

Language: Английский

Citations

3
Atroposelective Construction of Naphthylpyrazoles by Chiral Phosphoric Acid Catalyzed Enantioselective Cross‐Coupling of Pyrazoles with Naphthoquinone Esters DOI

Xi Luo,

Sen Li,

Yu‐Ting Tian

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(23)

Published: April 10, 2024

Abstract The catalytic asymmetric reaction of 5‐aminopyrazoles with naphthoquinone esters has been established. A wide range unprecedented axially chiral naphthylpyrazole derivatives (29 examples) have synthesized in moderate to excellent yields (up 99 % yield) enantioselectivities ee) by utilizing phosphoric acid as a catalyst. This protocol features mild conditions, broad substrate scope, good scalability and facile derivatization. Moreover, preliminary mechanistic investigation was conducted elucidate the mechanism.

Language: Английский

Citations

3
Convergent Azaspirocyclization of Bromoarenes with N-Tosylhydrazones by a Palladium Catalyst DOI

Aika Yanagimoto,

Yota Uwabe,

Qikun Wu

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(16), P. 10429 - 10435

Published: Aug. 6, 2021

1-Azaspirocyclic compounds have gained attention in chemistry and drug discovery fields. In this manuscript, the development of a Pd-catalyzed dearomative azaspirocyclization bromoarenes bearing an aminoalkyl group with N-tosylhydrazones is described. The present method enables introduction carbon substituents, achieving convergent synthesis 1-azaspirocycles. This allowed furan, thiophene, naphthalene cores to generate corresponding obtained azaspirocycles from furans were further elaborated via acid-catalyzed rearrangement afford 1-azaspirocyclopentenones.

Language: Английский

Citations

22
Cu(ii)/SPDO complex catalyzed asymmetric Baeyer–Villiger oxidation of 2-arylcyclobutanones and its application for the total synthesis of eupomatilones 5 and 6 DOI Creative Commons
Changsheng Zhang,

Ya-Ping Shao,

Fu‐Min Zhang

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(28), P. 8429 - 8435

Published: Jan. 1, 2022

A novel classical kinetic resolution of 2-aryl-substituted or 2,3-disubstituted cyclobutanones Baeyer-Villiger oxidation catalyzed by a Cu(ii)/SPDO complex is reported for the first time, producing normal lactones in excellent enantioselectivities (up to 96% ee) and regioselectivities >20/1), along with unreacted ketones 99% ee). The current transformation features wide substrate scope. Moreover, catalytic asymmetric total syntheses natural eupomatilones 5 6 are achieved nine steps from commercially available 3-methylcyclobutan-1-one.

Language: Английский

Citations

15