Cited by Donor–Acceptor Cyclopropane Ring Expansion to 1,2-Dihydronaphthalenes. Access to Bridged Seven-Membered Lactones

Donor‐Acceptor Cyclopropanes: Activation Enabled by a Single, Vinylogous Acceptor DOI

Nils L. Ahlburg,

Oliver Hergert,

Peter G. Jones

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(1)

Published: Nov. 2, 2022

A novel class of highly activated donor-acceptor cyclopropanes bearing only a single, vinylogous acceptor is presented. These strained moieties readily undergo cycloadditions with aldehydes, ketones, thioketones, nitriles, naphth-2-ols and various other substrates to yield the corresponding carbo- heterocycles. Diastereocontrol can be achieved through choice catalyst (Brønsted or Lewis acid). The formation tetrahydrofurans was shown enantiospecific when chiral are employed. series mechanistic kinetic experiments conducted elucidate plausible catalytic cycle rationalize stereochemical outcome.

Language: Английский

Citations

Synthesis of Heterocycles from Donor-Acceptor Cyclopropanes: A Five-Year Recap DOI

Ani Deepthi,

C.B. Meenakshy,

Maneesh Mohan

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(23), P. 3875 - 3894

Published: May 22, 2023

Abstract This review discusses the utility of donor-acceptor cyclopropanes (DACs) for construction heterocycles. In addition to (3+2), (3+3), and (4+3) cycloaddition pathways, nucleophilic ring-opening reactions, intramolecular transformations, cycloisomerizations in presence suitable catalysts pave way generation heterocycles from DACs. The mild reactions conditions employed variety starting materials that can be used as reaction partners make DAC route heterocycle synthesis attractive. literature covered this is period 2018 2023. 1 Introduction 2 Synthesis Nitrogen Heterocycles 2.1 By Annulations with Anthranils Azadienes 2.2 Nucleophilic Attack Anilines Hydrazones 2.3 Reaction Ureas Thioureas 2.4 Annulation Reactions Using an Azomethine Imine 2.5 Other 2.6 Transformations 3 Oxygen 3.1 Intramolecular 3.2 Intermolecular 4 Sulfur Selenium 4.1 Thiocarbonyl Substrates 4.2 Thio- Selenocyanates Thiosulfonate Salts 5 N–S N–O 6 Conclusions

Language: Английский

Citations

Iridium-Catalyzed Enantioselective Allylic Substitution of Vinylcyclopropanes by Carboxylic Acids DOI

Amit Singh Adhikari,

Soumen Pandit,

Ruchir Kant

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(9), P. 6261 - 6267

Published: April 21, 2023

An efficient method for a highly regio- and enantioselective allylic substitution of vinylcyclopropanes using carboxylic acids as oxygen nucleophile via iridium catalysis has been developed. This represents atom-economic approach the synthesis synthetically useful chiral building blocks in high yields. The practical utility this is demonstrated by application products transformations.

Language: Английский

Citations

[4+3]-Cycloaddition Reaction of Sulfilimines with Cyclobutenones: Access to Benzazepinones DOI

Xiaozhou Xie,

Jiangtao Sun

Organic Letters, Journal Year: 2021, Volume and Issue: 23(22), P. 8921 - 8925

Published: Nov. 1, 2021

A catalyst-free [4+3]-cycloaddition reaction of N-aryl sulfilimines with cyclobutenones is described, which provides a straightforward protocol for synthesizing 1,5-dihydro-2H-benzo[b]azepin-2-ones under mild conditions. This features broad substrate scope and good functional group tolerance does not require catalysts or additives. Moreover, using N-pyridinyl sulfilimine as the substrate, series pyridoazepinones have also been prepared.

Language: Английский

Citations

Copper-Catalyzed Asymmetric Nucleophilic Opening of 1,1,2,2-Tetrasubstituted Donor–Acceptor Cyclopropanes for the Synthesis of α-Tertiary Amines DOI

Shouang Lan,

Qinqin Cui,

Defu Luo

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 26, 2024

Catalytic asymmetric transformation of donor–acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy construct diverse types enantioenriched molecules. However, the use 1,1,2,2-tetrasubstituted DACs form products bearing quaternary stereocenters remains long-term unsolved challenge. Here, we report copper-catalyzed aminative ring opening tetrasubstituted alkynyl that delivers myriad α-tertiary amines with high levels enantioselectivities. The alkyne, amine, ester moieties within enable further applications, including synthesis bioactive Mechanistic studies indicate zwitterionic intermediate copper-acetylide unit plays key role in process, which represents new mode for achieving catalytic DACs.

Language: Английский

Citations

A DFT study of Ni-catalyzed (3 + 3)-annulation between donor–acceptor cyclopropanes and diaziridines DOI

Songshan Dai,

Xiaojiao Yang, Ran Fang

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(8), P. 1948 - 1958

Published: Jan. 1, 2023

The mechanism and stereoselectivity of the Ni-catalyzed [3 + 3] annulation between donor–acceptor cyclopropanes (DACs) diaziridines were rationalized by DFT calculations.

Language: Английский

Citations

Ytterbium Triflate-Catalyzed Intramolecular Arylative Ring Opening of Arylaminomethyl-Substituted Donor–Acceptor Cyclopropanes: Access to Tetrahydroquinolines DOI

Thangaraj Devaraj,

Kannupal Srinivasan

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 20, 2024

The treatment of arylaminomethyl-substituted donor-acceptor cyclopropanes with a catalytic amount Yb(OTf)

Language: Английский

Citations

Synthesis of Phosphoryl-Substituted Cyclopropanes Based on Cyano-Activated CH Acids. 1 : 2 Adduct-Product of O- and C-Alkylation of Dimedone DOI

G. Ts. Gasparyan, А. S. Bichakhchyan, L. V. Derdzyan

et al.

Russian Journal of General Chemistry, Journal Year: 2025, Volume and Issue: 95(5), P. 1086 - 1092

Published: May 1, 2025

Language: Английский

Citations

4‐(Dimethylamino)Pyridinium Azide in Protic Ionic Liquid Media as a Stable Equivalent of Hydrazoic Acid DOI

Иван А. Андреев, Maksim А. Boichenko, Нина К. Ратманова

et al.

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(14), P. 2403 - 2415

Published: June 16, 2022

Abstract We report a procedure for the multigram synthesis of 4‐(dimethylamino)pyridinium azide, stable, non‐explosive, low‐hygroscopic source azide ion soluble in both protic and aprotic organic solvents. In ionic liquid media this reagent was shown to serve as safer equivalent toxic unstable hydrazoic acid. The synthetic utility system demonstrated using donor‐acceptor cyclopropane ring opening model process. General procedures furnishing variety dialkyl (2‐azido‐2‐arylethyl)malonates or 4‐azido‐4‐arylbutyrates, depending on applied, were elaborated. conversion times studied cyclopropanes established providing relative reactivity sequence. application conventional nucleophilic substitution, oxirane opening, (3+2)‐cycloaddition (thio)cyano group well their combinations realized telescopic also demonstrated. magnified image

Language: Английский

Citations

Diastereoselective [3 + 2] Cycloaddition of Quinoxalin-2(1H)-ones with Donor–Acceptor Cyclopropanes: Efficient Synthesis of Tetrahydro pyrrolo[1,2-a]quinoxalin-4(5H)-ones DOI

Himangsu Sekhar Dutta,

Gulraız Ahmad,

Afsar Ali Khan

et al.

The Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 86(23), P. 16558 - 16572

Published: Nov. 15, 2021

A ytterbium triflate-catalyzed diastereoselective [3 + 2] cycloaddition of quinoxalinones with donor-acceptor cyclopropanes and cyclobutanes is described. series tetrahydropyrrolo-quinoxalinone derivatives were obtained in high yields (up to 96%) excellent diastereoselectivities 46:1). Other medicinally important heterocycles like benzoxazinone, isoquinoxalinone, dibenzoxazepine also suitable for the desired annulation reaction. The current method applicable scale-up Further, utility this reaction demonstrated by synthesis densely functionalized proline derivatives.

Language: Английский

Citations