Article
Chemistry, Multidisciplinary
Maxim S. Kobzev, Alexander A. Titov, Tatiana N. Borisova, Leonid G. Voskressensky, Alexey V. Varlamov, Massimo Christian D'Alterio, Alessio Petrone, Rafael Luque, Giovanni Talarico
Summary: This article presents a novel and original protocol for the preparation of complex framework compounds containing a vinylcyclopropane (VCP) fragment. The method involves UV conversion of cyclopentene (CP) derivatives under standard conditions to achieve high yields of target products. Additionally, a one-pot approach for the synthesis of VCPs and the mechanisms of mutual rearrangements of both VCP and CP have been rationalized using DFT calculations.
Article
Chemistry, Multidisciplinary
Gorka Garay, Josebe Hurtado, Manuel Pedron, Lorena Garcia, Efraim Reyes, Eduardo Sanchez-Diez, Tomas Tejero, Luisa Carrillo, Pedro Merino, Jose L. Vicario
Summary: We have demonstrated the catalytic and enantioselective rearrangement of vinylcyclopropane-cyclopentene, using (vinylcyclopropyl)acetaldehydes as starting materials and enamine intermediates for activation. The reaction involves the generation of a donor-acceptor cyclopropane, leading to the formation of an acyclic iminium ion/dienolate intermediate where stereochemistry is erased. The final cyclization step results in the stereocontrolled formation of various structurally distinct cyclopentenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Rajendra K. Mallick, Srinivas Vangara, Nagarjuna Kommu, Tirumaleswararao Guntreddi, Akhila K. Sahoo
Summary: This paper describes a novel Cu(II)-catalyzed rearrangement reaction for the synthesis of a series of synthetically important α-(m-substituted phenol)-α,β-unsaturated ketones, with a wide scope of functional group tolerance and synthetic viability. The synthesis of α,β-unsaturated ketones is also demonstrated in this study.
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, Multidisciplinary
Shintaro Ishida, Kengo Sakamoto, Ryo Kobayashi, Takeaki Iwamoto
Summary: This study reports the reactions of silanone with triarylboranes to form boroxysilanes. Experimental results and computational studies show that the electrophilicity of the unsaturated silicon atom is enhanced by the complexation of silanone with triarylboranes, and subsequent aryl migration from the boron atom to the electrophilic silicon atom takes place.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Philipp Zimmermann, Deniz Ar, Marie Roessler, Patrick Holze, Beatrice Cula, Christian Herwig, Christian Limberg
Summary: The synthesized Ni complexes, stabilized by Lewis-acidic cations, show a decreasing trend in CO2 activation within the Li, Na, and K series. The K+ ion has a significant impact on the stability and behavior of the Ni-CO22- entity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Keiichi Irifune, Ken Yamazaki, Takayuki Nakamuro, Masahiro Murakami, Tomoya Miura
Summary: A ligand-controlled regiodivergence in Ni-catalyzed rearrangement of vinylcyclopropanes to 1,4- or 1,5-disubstituted cyclopentenes is reported. The 1,4- or 1,5-disubstituted cyclopentene is selectively obtained depending on the choice of ligands. Detailed kinetic studies and density functional theory calculations on the catalytic cycle revealed that the product selectivity is determined at the reductive elimination step from the six-membered η(1)-allyl intermediate.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Hajime Maeda, Saki Nakamura, Taniyuki Furuyama, Masahito Segi
Summary: The reaction of 1-naphthyl naphthylmethyl ethers 1 and 2 with Lewis acids in CH2Cl2 resulted in rearrangement of the naphthylmethyl group to different positions of the naphthalene ring. The rearrangement of 2-naphthyl ethers 3 and 4 proceeded to the 1-position. Irradiation of compound 1 in benzene solution led to rearrangement at the 4-position, while rearrangement of compound 2 occurred at the 2- and 4-positions. The regioselectivity of the reactions can be explained by charge density, spin density, steric hindrance, and solvent cage effect.
JOURNAL OF MOLECULAR STRUCTURE
(2023)
Article
Chemistry, Applied
Xin Jin, Rusi Peng, Wen Tong, Jinpeng Yin, Hao Xu, Peng Wu
Summary: In the Beckmann rearrangement, TS-1 exhibits superior catalytic performance with silanol groups (including terminal silanols, hydrogen-bonded silanols, and silanol nests) as the active centers. Monolithic TS-1 microspheres (M-TS-1) show higher catalytic activity compared to conventional TS-1, and the diffusion properties of M-TS-1 can be further improved through chemical modifications to achieve longer reaction lifetime.
Article
Chemistry, Physical
Nikolai Bieniek, Sebastian Inacker, Norbert Hampp
Summary: Photochemical [2+2]-cycloadditions of coumarin-like monomers are widely studied for their photo-formation and photo-cleavage reactions. The study compares twelve coumarin-type cyclobutane dimers and identifies two with unexpectedly high quantum yield for cyclobutane cleavage. Electron donating substitutions, such as methoxy, decrease oxidation potential and make dimers sensitive towards oxidative dimer splitting. Among the investigated dimers, the methylated coumarin dimer is identified as the most promising for applications.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Jinxiu Xu, Yanji Song, Jia Yang, Bingqian Yang, Zhishan Su, Lili Lin, Xiaoming Feng
Summary: In this article, a highly diastereo- and enantioselective alpha-regioselective Mannich reaction is achieved by using chiral N,N'-dioxide/Sc-III catalysts. A series of chiral alpha-quaternary allyl aldehydes and homoallylic alcohols with vicinal multisubstituted stereocenters are constructed in excellent yields, good diastereomeric ratios, and excellent enantiomeric excess values. Experimental studies and DFT calculations reveal the critical factors for the alpha-regioselectivity to be the large steric hindrance of the ligand and the Boc protecting group of imines.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Shan-Shan Xun, Han Wang, Chang-Bin Yu, Sheng-Mei Lu, Yong-Gui Zhou
Summary: A diarylborinic acid-catalyzed ring opening reaction of cis-4-hydroxymethyl-1,2-cyclopentene oxides was developed, leading to the synthesis of 1,2,4-trisubstituted cyclopentane compounds containing a quaternary carbon center.
Article
Chemistry, Organic
Genki Horiguchi, Yohei Okada
Summary: Electrocatalytic reactions, induced by electron-catalyzed reactions using electrochemical methods, are a focus of interest in organic chemical synthesis. The study on radical cation vinylcyclopropane rearrangements showed that the desired rearrangement proceeded by a catalytic coulomb amount at the anode region via a radical cation chain mechanism, with the structure of the substrate playing a key role in the electrocatalytic rearrangement.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Qianchi Lin, Sujuan Zheng, Long Chen, Jin Wu, Jinzhao Li, Peizhi Liu, Shunxi Dong, Xiaohua Liu, Qian Peng, Xiaoming Feng
Summary: In this study, a highly enantioselective tandem reaction of alpha-alkynylketoamides with diarylphosphine oxides was achieved, leading to the synthesis of trisubstituted allenes with a diarylphosphinate functionality. The reaction showed broad substrate scope, high regio- and enantioselectivity, and good functional-group compatibility. The synthetic utility of the methodology was demonstrated by the conversion of products into complex bridged polycyclic architectures.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Arnaud Delbrassinne, Maximilien Richald, Julien Janssens, Raphael Robiette
Summary: A new rearrangement of vinylcyclopropane into skipped diene was reported, involving regioselective ring-opening and migration of substituents. The kinetic product of the process is the skipped diene, but formation of a more stable cyclopentene is also possible. Understanding the underlying processes allowed for the development of divergent methodologies to selectively and controlledly obtain cyclopentene or skipped diene from vinylcyclopropane.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(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, Multidisciplinary
A. E. Vartanova, A. Yu. Plodukhin, M. A. Boichenko, V. V. Shorokhov, S. S. Zhokhov, I. V. Trushkov, O. A. Ivanova
Summary: The rearrangement of 2,N-diaryl-1-carbamoylcyclopropanecarboxylates upon treatment with titanium(iv) chloride results in ring expansion and the formation of 1,5-diaryl-2-oxopyrrolidine-3-carboxylates. The ester group in the resulting products can be easily removed through either the Krapcho reaction or alkaline hydrolysis followed by thermal decarboxylation.
RUSSIAN CHEMICAL BULLETIN
(2022)
Article
Chemistry, Organic
Vitaly V. Shorokhov, Danila S. Lebedev, Maksim A. Boichenko, Sergey S. Zhokhov, Igor V. Trushkov, Olga A. Ivanova
Summary: A method for the synthesis of isoindoline derivatives was developed by using a domino reaction with a donor-acceptor cyclopropane and various primary amines. Under the hydrogenolysis conditions, the resulting N-benzyl-1,3-dihydroisoindole underwent selective cleavage of the exocyclic N-CH2Ar bond and followed by lactamization to form benzo[b]pyrrolizidinone. The same product can also be obtained by starting with reduction of the azidomethyl group at the ortho position of the donor aromatic substituent. Similarly, the generation of the o-2-aminoethyl group led to the formation of benzo[e]indolizidinone through two successive cyclization reactions.
CHEMISTRY OF HETEROCYCLIC COMPOUNDS
(2023)
Article
Chemistry, Physical
Nina K. Ratmanova, Ivan A. Andreev, Vitaly A. Shcherbinin, Olga A. Ivanova, Irina I. Levina, Victor N. Khrustalev, Igor V. Trushkov
Summary: Triple-role thiocyanate-containing protic ionic liquids (PILs) were used as a regenerable solvent, a Bronsted acid catalyst, and a nucleophile source to achieve the ring-opening of 1,3-indanedione-based donor-acceptor cyclopropanes.
JOURNAL OF MOLECULAR LIQUIDS
(2023)
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)
