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12 pages, 2027 KiB

Open AccessArticle

The TaCl₅-Mediated Reaction of Dimethyl 2-Phenylcyclopropane-1,1-dicarboxylate with Aromatic Aldehydes as a Route to Substituted Tetrahydronaphthalenes

by Tat’yana P. Zosim, Rita N. Kadikova, Roman A. Novikov, Alexander A. Korlyukov, Oleg S. Mozgovoj and Ilfir R. Ramazanov

Molecules 2024, 29(12), 2715; https://doi.org/10.3390/molecules29122715 - 7 Jun 2024

Cited by 2 | Viewed by 1215

Abstract

It is found that the reaction of dimethyl 2-phenylcyclopropane-1,1-dicarboxylate with 2 equivalents each of aromatic aldehydes and TaCl₅ in 1,2-dichloroethane at 23 °C for 24 h after hydrolysis gives substituted 4-phenyl-3,4-dihydronaphtalene-2,2(1H)-dicarboxylates in good yield. This represents a new type of [...] Read more.

It is found that the reaction of dimethyl 2-phenylcyclopropane-1,1-dicarboxylate with 2 equivalents each of aromatic aldehydes and TaCl₅ in 1,2-dichloroethane at 23 °C for 24 h after hydrolysis gives substituted 4-phenyl-3,4-dihydronaphtalene-2,2(1H)-dicarboxylates in good yield. This represents a new type of reactions between 2-arylcyclopropane-1,1-dicarboxylates and aromatic aldehydes, yielding chlorinated tetrahydronaphthalenes with a cis arrangement of the aryl and chlorine substituents in the cyclohexene moiety. A plausible reaction mechanism is proposed. Full article

(This article belongs to the Section Organic Chemistry)

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20 pages, 2678 KiB

Open AccessArticle

Nickel(II)-Catalyzed Formal [3+2] Cycloadditions between Indoles and Donor–Acceptor Cyclopropanes

by Víctor Quezada, Mariña Castroagudín, Felipe Verdugo, Sergio Ortiz, Guillermo Zaragoza, Fabiane M. Nachtigall, Francisco A. A. Reis, Alejandro Castro-Alvarez, Leonardo S. Santos and Ronald Nelson

Molecules 2024, 29(7), 1604; https://doi.org/10.3390/molecules29071604 - 3 Apr 2024

Viewed by 1998

Abstract

This article describes the development of a nickel-catalyzed regio- and diastereoselective formal [3+2] cycloaddition between N-substituted indoles and donor–acceptor cyclopropanes to synthesize cyclopenta[b]indoles. Optimized reaction conditions provide the desired nitrogen-containing cycloadducts in up to 93% yield and dr 8.6:1 with [...] Read more.

This article describes the development of a nickel-catalyzed regio- and diastereoselective formal [3+2] cycloaddition between N-substituted indoles and donor–acceptor cyclopropanes to synthesize cyclopenta[b]indoles. Optimized reaction conditions provide the desired nitrogen-containing cycloadducts in up to 93% yield and dr 8.6:1 with complete regioselectivity. The substrate scope showed high tolerance to various substituted indoles and cyclopropanes, resulting in the synthesis of six new cyclopenta[b]indoles and the isolation of five derivatives previously reported in the literature. In addition, a mechanistic proposal for the reaction was studied through online reaction monitoring by ESI-MS, allowing for the identification of the reactive intermediates in the Ni(II) catalyzed process. X-ray crystallography confirmed the structure and relative endo stereochemistry of the products. This method enables the fast and efficient construction of fused indolines from readily accessible starting materials. Full article

(This article belongs to the Special Issue Cyclization Reactions in Organic Synthesis: Recent Developments)

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6 pages, 579 KiB

Open AccessCommunication

Synthesis of 2-[2-(Ethoxymethoxy)phenyl]spiro[cyclopropane-1,2′-indene]-1′,3′-dione

by Olga A. Ivanova, Vitaly V. Shorokhov, Ivan A. Andreev, Nina K. Ratmanova, Victor B. Rybakov, Elena D. Strel’tsova and Igor V. Trushkov

Molbank 2023, 2023(1), M1604; https://doi.org/10.3390/M1604 - 14 Mar 2023

Cited by 1 | Viewed by 2409

Abstract

An 1,3-indanedione-derived donor–acceptor cyclopropane, bearing the ethoxymethyl-protected phenolic group at the ortho-position of the donor aryl substituent, has been synthesized using a reaction sequence involving the Knoevenagel condensation of 1,3-indanedione with the corresponding protected salicylaldehyde followed by the Corey–Chaykovsky cyclopropanation of the [...] Read more.

An 1,3-indanedione-derived donor–acceptor cyclopropane, bearing the ethoxymethyl-protected phenolic group at the ortho-position of the donor aryl substituent, has been synthesized using a reaction sequence involving the Knoevenagel condensation of 1,3-indanedione with the corresponding protected salicylaldehyde followed by the Corey–Chaykovsky cyclopropanation of the obtained adduct with dimethylsulfoxonium methylide. The structure of the synthesized cyclopropane was unambiguously proved by single-crystal X-ray diffraction data. Full article

(This article belongs to the Section Organic Synthesis and Biosynthesis)

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21 pages, 2017 KiB

Open AccessArticle

Synthesis of 1,5-Substituted Pyrrolidin-2-ones from Donor–Acceptor Cyclopropanes and Anilines/Benzylamines

by Maksim A. Boichenko, Andrey Yu. Plodukhin, Vitaly V. Shorokhov, Danyla S. Lebedev, Anastasya V. Filippova, Sergey S. Zhokhov, Elena A. Tarasenko, Victor B. Rybakov, Igor V. Trushkov and Olga A. Ivanova

Molecules 2022, 27(23), 8468; https://doi.org/10.3390/molecules27238468 - 2 Dec 2022

Cited by 8 | Viewed by 4776

Abstract

We developed a straightforward synthetic route to pharmacologically important 1,5-substituted pyrrolidin-2-ones from donor–acceptor cyclopropanes bearing an ester group as one of the acceptor substituents. This method includes a Lewis acid-catalyzed opening of the donor–acceptor cyclopropane with primary amines (anilines, benzylamines, etc.) to γ-amino [...] Read more.

We developed a straightforward synthetic route to pharmacologically important 1,5-substituted pyrrolidin-2-ones from donor–acceptor cyclopropanes bearing an ester group as one of the acceptor substituents. This method includes a Lewis acid-catalyzed opening of the donor–acceptor cyclopropane with primary amines (anilines, benzylamines, etc.) to γ-amino esters, followed by in situ lactamization and dealkoxycarbonylation. The reaction has a broad scope of applicability; a variety of substituted anilines, benzylamines, and other primary amines as well as a wide range of donor–acceptor cyclopropanes bearing (hetero)aromatic or alkenyl donor groups and various acceptor substituents can be involved in this transformation. In this process, donor–acceptor cyclopropanes react as 1,4-C,C-dielectrophiles, and amines react as 1,1-dinucleophiles. The resulting di- and trisubstituted pyrrolidin-2-ones can be also used in subsequent chemistry to obtain various nitrogen-containing polycyclic compounds of interest to medicinal chemistry and pharmacology, such as benz[g]indolizidine derivatives. Full article

(This article belongs to the Special Issue Recent Developments in the Synthesis and Functionalization of Nitrogen Heterocycles)

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15 pages, 1540 KiB

Open AccessCommunication

Synthesis of (Het)aryl 2-(2-hydroxyaryl)cyclopropyl Ketones

by Alexander A. Fadeev, Alexey O. Chagarovskiy, Anton S. Makarov, Irina I. Levina, Olga A. Ivanova, Maxim G. Uchuskin and Igor V. Trushkov

Molecules 2020, 25(23), 5748; https://doi.org/10.3390/molecules25235748 - 5 Dec 2020

Cited by 4 | Viewed by 4296

Abstract

A simple general method for the synthesis of 1-acyl-2-(ortho-hydroxyaryl)cyclopropanes, which belong to the donor–acceptor cyclopropane family, has been developed. This method, based on the Corey–Chaykovsky cyclopropanation of 2-hydroxychalcones, allows for the preparation of a large diversity of hydroxy-substituted cyclopropanes, which can [...] Read more.

A simple general method for the synthesis of 1-acyl-2-(ortho-hydroxyaryl)cyclopropanes, which belong to the donor–acceptor cyclopropane family, has been developed. This method, based on the Corey–Chaykovsky cyclopropanation of 2-hydroxychalcones, allows for the preparation of a large diversity of hydroxy-substituted cyclopropanes, which can serve as promising building blocks for the synthesis of various bioactive compounds. Full article

(This article belongs to the Special Issue Advances in Organic Synthesis: A Theme Issue in Honor of Professor Mieczysław Mąkosza)

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8 pages, 1171 KiB

Open AccessCommunication

Dimethyl 2-{[2-(2-Methoxy-1-methoxycarbonyl-2-oxoethyl)-4,5,7-trimethoxy-3-(2,4,5-trimethoxyphenyl)-2,3-dihydro-1H-inden-1-yl]methyl}malonate

by Maksim A. Boichenko, Alexey O. Chagarovskiy, Victor B. Rybakov, Igor V. Trushkov and Olga A. Ivanova

Molbank 2020, 2020(1), M1107; https://doi.org/10.3390/M1107 - 14 Jan 2020

Viewed by 3164

Abstract

A simple synthetic approach to dimethyl 2-{[2-(2-methoxy-1-methoxycarbonyl-2-oxoethyl)-4,5,7-trimethoxy-3-(2,4,5-trimethoxyphenyl)-2,3-dihydro-1H-inden-1-yl]methyl}malonate has been developed, based on a B(C₆F₅)₃-induced domino dimerization of 2-(2,4,5-trimethoxyphenyl)cyclopropane-1,1-diester. Full article

(This article belongs to the Section Organic Synthesis and Biosynthesis)

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7 pages, 602 KiB

Open AccessCommunication

4b,5,6,9-Tetrahydro-7H-dibenzo[c,e]pyrrolo[1,2-a]azepin-7-one

by Maksim A. Boichenko, Igor Yu. Babkin, Sergey G. Kobylskoy, Alexey O. Chagarovskiy, Olga A. Ivanova and Igor V. Trushkov

Molbank 2019, 2019(2), M1061; https://doi.org/10.3390/M1061 - 17 May 2019

Cited by 1 | Viewed by 3064

Abstract

A simple approach to synthesize 4b,5,6,9-tetrahydro-7H-dibenzo[c,e]pyrrolo[1,2-a]azepin- 7-one has been developed, based on a three-step transformation of 2-(2-bromophenyl)cyclopropane-1,1-diester. The key stage in this method is an intramolecular cross-coupling of 1-(2-bromobenzyl)-5-(2-bromophenyl)pyrrolidin-2-one under continuous flow conditions in an H-Сube-Pro using commercially available supported Pd catalysts. Full article

(This article belongs to the Collection Molecules from Catalytic Processes)

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11 pages, 3115 KiB

Open AccessCommunication

Convenient Synthesis of Functionalized Cyclopropa[c]coumarin-1a-carboxylates

by Olga A. Ivanova, Vladimir A. Andronov, Irina I. Levina, Alexey O. Chagarovskiy, Leonid G. Voskressensky and Igor V. Trushkov

Molecules 2019, 24(1), 57; https://doi.org/10.3390/molecules24010057 - 24 Dec 2018

Cited by 13 | Viewed by 3953

Abstract

A simple method has been developed for the synthesis of cyclopropa[c]coumarins, which belong to the donor-acceptor cyclopropane family and, therefore, are promising substrates for the preparation of chromene-based fine chemicals. The method, based on the acetic acid-induced intramolecular transesterification of 2-arylcyclopropane-1,1-dicarboxylates, [...] Read more.

A simple method has been developed for the synthesis of cyclopropa[c]coumarins, which belong to the donor-acceptor cyclopropane family and, therefore, are promising substrates for the preparation of chromene-based fine chemicals. The method, based on the acetic acid-induced intramolecular transesterification of 2-arylcyclopropane-1,1-dicarboxylates, was found to be efficient for substrates containing hydroxy group directly attached to the aromatic ring. Full article

(This article belongs to the Special Issue New Studies on the Synthesis of Biologically Active Products)

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