Article
Chemistry, Organic
Matteo Faltracco, Matteo Damian, Eelco Ruijter
Summary: In this study, a cascade reaction involving indolecarboxaldehydes and phosphonate-functionalized donor-acceptor cyclopropanes was used to synthesize functionalized dihydrocarbazoles and cyclohepta[cd]indoles in formal (3 + 3) and (4 + 3) cycloadditions. A slight modification to the reaction conditions also enabled access to fully aromatic heterocyclic scaffolds through the thermal loss of an electron-rich aryl moiety.
Article
Chemistry, Multidisciplinary
Nils L. Ahlburg, Oliver Hergert, Peter G. Jones, Daniel B. Werz
Summary: A novel class of highly activated donor-acceptor cyclopropanes with a single vinylogous acceptor is presented. These moieties undergo cycloaddition reactions with various substrates to form carbo- and heterocycles. The stereochemical outcome can be controlled by the choice of catalyst. Mechanistic and kinetic experiments were conducted to explain the catalytic cycle and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Ani Deepthi, C. B. C. Meenakshy, Maneesh Mohan
Summary: This review discusses the use of donor-acceptor cyclopropanes (DACs) for building heterocycles. The generation of heterocycles from DACs can be achieved through (3+2), (3+3), and (4+3) cycloaddition pathways, as well as nucleophilic ring-opening reactions, intramolecular transformations, and cycloisomerizations with suitable catalysts. The mild reaction conditions and the wide range of starting materials make the DAC route attractive for heterocycle synthesis. The literature covered in this review spans from 2018 to 2023.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cascade reaction catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate. The reaction proceeds under mild conditions and provides the desired products in high yields and enantioretention. Furthermore, these dihydro-3H-carbazole-2-carboxylates can be transformed into decarboxylated compounds through hydrolysis and decarboxylation under unexpectedly mild reaction conditions, giving moderate yields with high retention of enantiomeric purity.
Article
Chemistry, Organic
Prasoon Raj Singh, Pratibha Kalaramna, Shamsad Ali, Avijit Goswami
Summary: A simple protocol has been developed to access thio-/selenopyrrolines through a (3+2)-cycloaddition reaction using SnCl4 as a Lewis acid catalyst. Good chemoselectivity was observed when DACs were treated, indicating that thiocyanate is more reactive than nitrile moiety in such reactions.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Anu Jacob, Philip Barkawitz, Peter G. Jones, Daniel B. Werz
Summary: A facile and efficient route to dithiolanes starting from donor-acceptor cyclopropanes has been developed. Potassium p-toluenethiosulfonate has been established as the optimal reagent for this reaction. The methodology allows for the synthesis of dithiolanes in moderate to good yields with high functional group tolerance.
Article
Chemistry, Physical
Ming Bao, Karlos Lopez, Raj Gurung, Hadi Arman, Michael P. Doyle
Summary: A highly enantioselective synthesis of chiral dihydro-3H-carbazole-2-carboxylate derivatives is achieved via a one-pot cyclopentannulation-rearrangement cascade reaction. The reaction is catalyzed by nickel(II) perchlorate hexahydrate and scandium(III) trifluoromethanesulfonate, and involves the use of 3-methylindole and non-racemic donor-acceptor cyclopropanes. The resulting products show high yields and enantioretention under mild reaction conditions, and further transformation into decarboxylated compounds can be achieved with moderate yields and high enantiomeric purity.
Article
Chemistry, Multidisciplinary
Stefano Nicolai, Jerome Waser
Summary: This study reports a Lewis acid catalyzed (4+3) annulative addition reaction for the efficient synthesis of densely substituted azepanes. The reaction achieved good yields and high diastereoselectivity under mild conditions using ytterbium triflate or copper triflate with a trisoxazoline ligand as the catalyst. The obtained cycloadducts were convenient substrates for further modifications.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Simon Kolb, Nils L. Ahlburg, Daniel B. Werz
Summary: A new electrochemical method has been described for the functionalization of donor-acceptor cyclopropanes and cyclobutanes with arenes using Friedel-Crafts-type reactivity. The catalyst-free strategy relies on direct anodic oxidation of strained carbocycles, leading to the formation of radical cations that act as electrophiles for the arylation reaction. Broad reaction scopes for cyclopropanes, cyclobutanes, and aromatic reaction partners are presented, along with a proposed electrolysis mechanism.
Article
Chemistry, Organic
Anu Jacob, Peter G. G. Jones, Daniel B. B. Werz
Summary: A new method for synthesizing tetrahydroselenophenes with exocyclic double bonds was reported, which involves the reaction of donor-acceptor cyclopropanes (DACs) with lithium alkynylselenolates in the presence of In(OTf)3. The method has a broad substrate scope and high yields.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Murugesan Thangamani, Kannupal Srinivasan
Summary: This method utilizes aroyl-substituted donor-acceptor (D-A) cyclopropanes and 1-naphthylamines as substrates, leading to the synthesis of dibenzo[c,h]acridines through nucleophilic ring-opening and subsequent fragmentation and cyclization reactions with reasonable substrate scope and 50-70% yields.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Gwyndaf A. Oliver, Daniel B. Werz
Summary: A general method for the 1,3-bisfunctionalization of D-A cyclopropanes using sulfinate salts and electrophilic fluorination reagents is presented. This method involves Lewis acid catalysis, nucleophilic ring-opening by the sulfinate anion, and trapping of electrophilic fluorine to form gamma-fluorosulfones. This is the first one-step synthesis of sulfones fluorinated in the gamma-position from a carbon backbone, according to our knowledge.
Article
Chemistry, Organic
Grzegorz Mloston, Mateusz Kowalczyk, Andre U. Augustin, Peter G. Jones, Daniel B. Werz
Summary: The reactivity of donor-acceptor cyclopropanes towards thioketenes was investigated, leading to the formation of exocyclic thioenol ethers in moderate to good yields in a (3+2)-cycloaddition using Sc(OTf)(3) as a Lewis acidic catalyst. Unsymmetrical thioketenes provided E/Z mixtures at the double bond, with the Z isomer being preferred.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Xinyi Wan, Shan Wang, Chengjun Wu, Jianbo Gan, Cunde Wang
Summary: The synthesis of polysubstituted quinolines was investigated through a Yb(OTf)(3)-mediated annulation of cyclopropane-1,1-dicarbonitriles and 2-aminobenzaldehydes, resulting in generally good yields. The cascade reaction involves ring opening, intermolecular nucleophilic addition, intramolecular nucleophilic addition, and demalononitrile aromatization, with the malononitrile group acting as a removable directing group mediated by Yb(OTf)(3).
Review
Chemistry, Organic
Liangliang Yang, Haiyang Wang, Ming Lang, Shiyong Peng
Summary: This short review summarizes the recent impressive developments on the high-order dipolar annulations of donor-acceptor cyclopropanes and cyclobutanes to afford medium-sized (hetero)cycles.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Maksim A. Boichenko, Ivan A. Andreev, Alexey O. Chagarovskiy, Irma I. Levina, Sergey S. Zhokhov, Igor V. Trushkov, Olga A. Ivanova
JOURNAL OF ORGANIC CHEMISTRY
(2020)
Article
Chemistry, Organic
Elena Y. Zelina, Tatyana A. Nevolina, Ludmila N. Sorotskaja, Dmitry A. Skvortsov, Igor Trushkov, Maxim G. Uchuskin
TETRAHEDRON LETTERS
(2020)
Article
Chemistry, Multidisciplinary
Ivan A. Andreev, Nina K. Ratmanova, Andre U. Augustin, Olga A. Ivanova, Irina I. Levina, Victor N. Khrustalev, Daniel B. Werz, Igor V. Trushkov
Summary: In this study, a new concept of the triple role of protic ionic liquids with nucleophilic anions was proposed, demonstrating their efficiency in ring-opening reactions of donor-acceptor cyclopropanes. The ability of thiocyanate-based protic ionic liquids to serve as a regenerable solvent, a Bronsted acid for catalysis, and a source of nucleophile was exemplified through various organic transformations under mild metal-free conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Biochemistry & Molecular Biology
Alexander A. Fadeev, Alexey O. Chagarovskiy, Anton S. Makarov, Irina I. Levina, Olga A. Ivanova, Maxim G. Uchuskin, Igor Trushkov
Article
Biochemistry & Molecular Biology
Roman O. Shcherbakov, Diana A. Eshmemet'eva, Anton A. Merkushev, Igor V. Trushkov, Maxim G. Uchuskin
Summary: A new approach to 3-(furan-2-yl)-1,3-di(het)arylprop-2-en-1-ones has been developed through the oxidative dearomatization and cyclization of di(het)aryl-substituted 2-ene-1,4,7-triones, showing high synthetic efficiency.
Article
Chemistry, Organic
Anna E. Vartanova, Irina I. Levina, Victor B. Rybakov, Olga A. Ivanova, Igor Trushkov
Summary: This study discovered that a reaction between donor-acceptor cyclopropanes and 6-amino-1,3-dimethyluracil catalyzed by scandium trifluoromethanesulfonate proceeds via a three-membered ring opening mechanism, leading to the formation of 6,7-dihydro-1H-pyrimido[4,5-b]-azepine-2,4,8-triones under basic conditions. This reaction pathway produces an interesting subclass of nucleobase analogues.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Organic
Petrakis N. Chalikidi, Taimuraz T. Magkoev, Andrey V. Gutnov, Oleg P. Demidov, Maxim G. Uchuskin, Igor V. Trushkov, Vladimir T. Abaev
Summary: Two approaches have been developed for the synthesis of substituted phosphonium salts from easily available benzyl alcohols and their heterocyclic analogs. The direct mixing method is more efficient for acid-sensitive substrates, while the one-pot procedure is better for benzyl alcohols with electroneutral or electron-withdrawing substituents.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Anna E. Vartanova, Andrey Yu Plodukhin, Nina K. Ratmanova, Ivan A. Andreev, Mikhail N. Anisimov, Nikita B. Gudimchuk, Victor B. Rybakov, Irina I. Levina, Olga A. Ivanova, Igor Trushkov, Igor Alabugin
Summary: This study expands the limits of endo-tet cyclizations by showing that donor-acceptor cyclopropanes can form a seven-membered ring via a genuine 6-endo-tet process, yielding tetrahydrobenz[b]azepin-2-ones. Control of the stereochemistry of the products through reaction conditions allows access to both diastereomers.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Alexander A. Fadeev, Anton S. Makarov, Olga A. Ivanova, Maxim G. Uchuskin, Igor Trushkov
Summary: The divergent synthesis of benzannulated 2,8-dioxabicyclo[3.2.1]octanes and 2,3-dihydrobenzofurans using extended Corey-Chaykovsky reactions demonstrates the potential of this method in producing products with crucially different heterocyclic skeletons from the same starting compounds.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Applied
Ivan A. Andreev, Maksim A. Boichenko, Nina K. Ratmanova, Olga A. Ivanova, Irina I. Levina, Victor N. Khrustalev, Igor A. Sedov, Igor Trushkov
Summary: A new method for the synthesis of 4-(dimethylamino)pyridinium azide was reported, which is a stable and non-explosive source of azide ion soluble in organic solvents. In protic ionic liquid media, this reagent serves as a safer alternative to toxic and unstable hydrazoic acid. The synthetic utility of this method was demonstrated using a model reaction, showing its wide range of applications.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Biochemistry & Molecular Biology
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, Olga A. Ivanova
Summary: We developed a straightforward synthetic route to important pyrrolidin-2-one compounds from donor-acceptor cyclopropanes. This method has a broad applicability, allowing the synthesis of compounds by using various amines and donor-acceptor cyclopropanes.
Article
Chemistry, Organic
Olga A. A. Ivanova, Vitaly V. V. Shorokhov, Ivan A. A. Andreev, Nina K. K. Ratmanova, Victor B. B. Rybakov, Elena D. D. Strel'tsova, Igor V. V. Trushkov
Summary: A donor-acceptor cyclopropane, derived from 1,3-indanedione and bearing an ortho-ethoxymethyl-protected phenolic group at the donor aryl substituent, was synthesized through a reaction sequence involving Knoevenagel condensation and Corey-Chaykovsky cyclopropanation. The structure of the synthesized cyclopropane was confirmed by single-crystal X-ray diffraction analysis.
Article
Chemistry, Organic
Vitaly V. Shorokhov, Sergey S. Zhokhov, Victor B. Rybakov, Maksim A. Boichenko, Ivan A. Andreev, Nina K. Ratmanova, Igor V. Trushkov, Olga A. Ivanova
Summary: A Lewis acid-promoted domino ring-opening cyclization of readily available donor-acceptor cyclopropanes with a preinstalled electrophilic center, embedded in a donor group, to functionalized 1,2-dihydronaphthalenes is reported. The obtained compounds are transformed to pharmacologically attractive bridged tricyclic esters in a diastereospecific manner.
Article
Chemistry, Organic
Anna E. Vartanova, Irina I. Levina, Nina K. Ratmanova, Ivan A. Andreev, Olga A. Ivanova, Igor Trushkov
Summary: This study investigated the Lewis acid-catalysed reactions of donor-acceptor cyclopropanes with 1,3-disubstituted 5-aminopyrazoles. It was found that under the catalysis of gallium(iii) chloride, the nucleophilic attack of the exocyclic amino group led to the chemoselective three-membered ring opening. On the other hand, in the presence of scandium(iii) triflate, N-alkylation, C(4)-alkylation, or a mixture of both reactions occurred. The C(4)-alkylation products were further transformed into tetrahydropyrazolo[3,4-b]azepines, which have potential applications in medicinal chemistry and pharmacology.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Organic
Maksim A. Boichenko, Igor Yu Babkin, Sergey G. Kobylskoy, Alexey O. Chagarovskiy, Olga A. Ivanova, Igor Trushkov
