Article
Chemistry, Multidisciplinary
Marc Devillard, Nour Nour Eddine, Marie Cordier, Gilles Alcaraz
Summary: A straightforward synthetic methodology for the preparation of photochromic siloles based on the dithienylethene motif has been developed. This method relies on an efficient palladium-catalyzed annulation reaction of a 2,3-bis(3-thienyl)-silirene with terminal alkynes in mild conditions. The reaction is functional group-tolerant and can be extended to the synthesis of photochromic polymers with different degrees of photochromic unit incorporation by adjusting the polymer/silirene stoichiometric ratio.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Quentin Dherbassy, Srimanta Manna, Chunling Shi, Watcharapon Prasitwatcharakorn, Giacomo E. M. Crisenza, Gregory J. P. Perry, David J. Procter
Summary: In this study, an enantioselective copper-catalyzed borylative cyclization was reported for the assembly of privileged pyrroloquinazolinone motifs. The reaction demonstrated high enantio- and diastereocontrol, yielding products with quaternary stereocenters. The utility of the products was further demonstrated through additional manipulations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jie Wang, Shan-Shan Wang, Jun Xiao, Yu-Jie He, Xin-Yan Wu, Xingguang Li, Pei-Nian Liu
Summary: CF3-substituted imidoyl sulfoxonium ylides (TFISYs) are versatile and powerful synthons for the synthesis of diverse CF3-substituted N-heterocycles, offering broad application prospects.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Siti Nur Fairuz Binte Sheikh Ismail, Binmiao Yang, Yu Zhao
Summary: In this study, a highly diastereo- and enantioselective Pd-catalyzed [4 + 2] cycloaddition of benzofuran-derived azadienes with vinyl benzoxazinanones was successfully achieved, leading to the construction of a novel spirocyclic tetrahydroquinoline scaffold with high stereoselectivity.
Article
Chemistry, Multidisciplinary
Tobias Wagener, Lukas Lueckemeier, Constantin G. Daniliuc, Frank Glorius
Summary: This study successfully demonstrates the synthesis of sought-after, enantioenriched delta-lactams through an interrupted hydrogenation mechanism using oxazolidinone-substituted pyridines and water.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Chao Shan, Jinping Xu, Liming Cao, Chaoming Liang, Ruihua Cheng, Xiantong Yao, Maolin Sun, Jinxing Ye
Summary: This study developed a practical continuous flow protocol for efficient synthesis of various functionalized piperidines within minutes, with high yields and enantiomeric excess. The scalability and utility of the process were demonstrated through the efficient synthesis of a drug precursor.
Review
Chemistry, Applied
Seoung-Mi Choi, Ju Hyun Kim
Summary: This review summarizes the progress made in the synthesis of 2H-pyrroles since 2000, including methods such as dearomatization of 1H-pyrrole, oxidation of pyrrolines or pyrrolidines, ring construction via catalytic cycloaddition, and rearrangement of 3H-pyrroles.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Xiaoxiang Zhang, Yingying Zhang, Xiaoting Gu, Zhuan Zhang, Wanxing Wei, Taoyuan Liang
Summary: A copper-mediated 2,3-difunctionalization of indoles to afford 3-halogenated 2,3 '-biindoles is described. The protocol uses readily available feedstocks and a naturally abundant copper catalyst system, which allows the regioselective formation of C-C and C-X (X = Cl & Br) bonds in one single operation. Copper metal salt serves not only as a catalyst but also as a reactant to provide the source of halogen, avoiding the use of environmentally unfriendly reagents and displaying good functional group compatibility.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Davit Hayrapetyan, Valeriya Stepanova
Summary: In this study, spirocyclic pyrrolidones and piperidones were synthesized via [3+2]- and [3+3]-aza-annulation reactions starting from readily available alpha-ketolactones and alpha-ketolactams. The annulation reactions proceeded with good yields and excellent diastereoselectivity, creating one C-C and two C-N bonds, as well as three new stereocenters in a fast and efficient manner.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Lin-Jun Qi, Cui-Ting Li, Zheng-Qi Huang, Jia-Tian Jiang, Xin-Qi Zhu, Xin Lu, Long-Wu Ye
Summary: The study presents a novel copper-catalyzed asymmetric formal annulation reaction, which can synthesize a range of chiral oxygen-heterocycles via carbonyl ylides with excellent enantioselectivity and yields.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Luke R. Odell, Bobo Skillinghaug, Christof Matt, Peng Wu, Tobias Koolmeister, Matthieu Desroses, Sabin Llona-Minguez, Olov Wallner, Thomas Helleday, Martin Scobie
Summary: Here, we describe the development of a new cascade reaction for the synthesis of rare indazole acetic acid scaffolds. By heating 3-amino-3-(2-nitroaryl)propanoic acids with an appropriate nucleophile/solvent under basic conditions, three distinct indazole acetic acid derivatives (unsubstituted, hydroxy, and alkoxy) can be conveniently synthesized. The reaction can tolerate various functional groups and electronic effects, resulting in the synthesis and characterization of 23 novel indazole acetic acids. This work provides a valuable synthetic strategy for drug discovery programs.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Applied
Dimitris Matiadis
Summary: 2-Pyrazolines are important five-membered heterocycles with two adjacent nitrogen atoms. They have various functional groups and unique biological properties, and are used as building blocks. In recent years, there has been significant progress in the synthesis of 2-pyrazolines, with the development of novel strategies and improvements of existing protocols. This review summarizes the synthetic methodologies from 2012 to 2022, discussing the challenges, capabilities, scopes, and limitations of the reactions, as well as substitution patterns and mechanisms where applicable.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Martin S. Faillace, Noelia M. Ceballos, Natalia B. Shustova, Walter J. Pelaez
Summary: In this study, a regiospecific and stereoselective synthesis method for novel pyrrolo thioxoimidazolidinones with promising biological activities was reported. These compounds have great potential applications due to the pharmaceutical properties of the thioxoimidazolidinone core. The reaction between different thioxoimidazolidinones and trans-4-ethoxy-1,1,1-trifluorobut-3-en-2-one (ETFBO) yielded bicyclic 1,3-diaza heterocycles with a trifluoromethyl (CF3) moiety. Both experimental analysis and theoretical calculations were conducted to reveal the reaction mode of this building block and the underlying mechanism for the observed reactions. Remarkably, the unusual mechanism retained the ethanol moiety from the building block in the final products, deviating from conventional nucleophilic reactions reported in the literature.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Ting Chen, Bin Tan, Zhi Huang, Guojiang Mao, Shanping Chen, Guo-Jun Deng
Summary: A facile method for the rapid synthesis of benzoacridines is described in this paper. This protocol, promoted by p-toluenesulfonic acid, starts from aromatic aldehydes and N-phenyl naphthylamines, and yields a variety of benzoacridines in 30-90% under metal-free conditions. The present approach involves a cascade of condensation, Friedel-Crafts alkylation, annulation, and dehydroaromatization in one pot.
CHEMISTRY & BIODIVERSITY
(2023)
Article
Chemistry, Physical
Philip R. D. Murray, Isabelle Nathalie-Marie Leibler, Sandrine M. Hell, Eris Villalona, Abigail G. Doyle, Robert R. Knowles
Summary: We introduce a two-component annulation strategy that involves the combination of aryl alkenes and redox-active radical precursors bearing tethered nucleophiles, enabling the synthesis of a diverse collection of five- and six-membered saturated heterocycles. This strategy employs an Ir(III) photocatalyst and a Bronsted acid under visible-light irradiation. The synthesis involves reductive proton-coupled electron transfer, radical addition to alkene, oxidative radical-polar crossover, and cyclization of the tethered nucleophile. This approach allows the easy access to a wide range of heterocycles, including pyrrolidines, piperidines, tetrahydrofurans, morpholines, delta-valerolactones, and dioxanones. It is amenable to gram-scale preparation and complex fragment coupling.
Article
Chemistry, Multidisciplinary
Yusuke Masuda, Hiromu Tsuda, Masahiro Murakami
Summary: This unique photoinduced reaction couples a triarylphosphine, an alkene, and water to produce a novel compound, increasing molecular complexity and applicability to the Wittig olefination reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Masahiro Murakami
Summary: This essay highlights the life and contributions of Professor Teruaki Mukaiyama, emphasizing his insightful mentorship and significant scientific impact on the chemical community. It serves as a lasting tribute to his didactic guidance and encouragement for future generations.
Article
Chemistry, Multidisciplinary
Tomoya Miura, Naoki Oku, Yota Shiratori, Yuuya Nagata, Masahiro Murakami
Summary: A new method for constructing propionate-derived trisubstituted alkene motifs with stereoselectivity has been reported. The method involves the ruthenium(II)-catalyzed double-bond transposition of 1-substituted 1,1-di(pinacolatoboryl)-alk-3-enes to generate E isomers of anti-homoallylic alcohols, while using a dimeric palladium(I) complex leads to the formation of Z isomers. The motifs can be successfully applied to the syntheses of specific compounds.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Lantao Liu, Fangyuan Cheng, Chenxiang Meng, An-An Zhang, Mingliang Zhang, Kai Xu, Naoki Ishida, Masahiro Murakami
Summary: A Pd-catalyzed chemo-, regio-, and enantioselective ring-closing/ring-opening cross coupling reaction has been developed with diverse aryl halide-tethered alkenes and benzocyclobutenols as substrates. This method provides a convenient approach to chiral 2,3-dihydrobenzofurans with excellent enantioselectivities, and has been applied in the concise synthesis of analogues of cannabinoid receptor 2 agonists.
Article
Chemistry, Multidisciplinary
Tomoya Miura, Shunsuke Moritani, Yota Shiratori, Masahiro Murakami
Summary: A unique method for the synthesis of substituted 1-naphthols through rhodium(ii)-catalysed ring-expansion reaction of 2-triazolyl-1-indanone derivatives is reported. The 1,2-acyl migration occurs with an intermediate alpha-imino rhodium carbenoid generated from the triazolyl moiety.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Tomoya Miura, Yumi Ishihara, Takayuki Nakamuro, Shunsuke Moritani, Yuuya Nagata, Masahiro Murakami
Summary: This study investigates the asymmetric cyclooligomerization of bifunctional monomers catalyzed by rhodium(II). The major products obtained are cyclic dimers with unique structures, and it is observed that these structures can undergo ring-flipping.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Organic
Yusuke Masuda, Masumi Uno, Masahiro Murakami
Summary: This study reports a photoinduced reaction of triarylphosphines with alkenes in the presence of carbonic acid, leading to the formation of fused tricyclic phosphonium salts with a phosphatricyclo[4.3.0.0(2.9)]nonene core structure. The reaction involves dearomatizing transannulation of the phenyl ring, 1,2-migration of the phosphorus atom, and incorporation of an alkene, being promoted by cooperation of visible light with a photocatalyst under mild reaction conditions.
Article
Chemistry, Organic
Naoki Oku, Masahiro Murakami, Tomoya Miura
Summary: This article introduces a Suzuki-Miyaura cross-coupling reaction of alpha-chloroacetates or alpha-chloroacetamides with arylboronic acids under visible-light irradiation, providing a mild method for the synthesis of alpha-arylacetates and alpha-arylacetamides. Additionally, the authors successfully synthesized a key intermediate of the plant hormone auxin, indole-3-acetic acid derivative, from 1-Boc-indole in two steps by combining an iridium-catalyzed C-H borylation and a palladium-catalyzed cross-coupling reaction.
Article
Chemistry, Organic
Daichi Ikeshita, Yusuke Masuda, Naoki Ishida, Masahiro Murakami
Summary: A photoinduced hydrophosphination reaction of terminal alkynes with tri(o-tolyl)phosphine to form alkenylphosphonium salts is reported herein. This sustainable reaction eliminates the need for complex starting materials and expensive transition metals. The o-methyl groups of tri(o-tolyl)phosphine serve two important roles in guiding the phosphorus radical addition onto the terminal sp carbon and intramolecular hydrogen atom transfer.
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, Organic
Naoki Oku, Tomoya Miura
Summary: A double C(sp3)-H functionalization of ethylarenes with alcohols and N- fluorobenzenesulfonimide is demonstrated. The reaction proceeds in three stages: (1) Cu-catalyzed benzylic alkoxylation of ethylarenes to give 1-(1-alkoxyethyl)benzenes; (2) The resulting 1-(1-alkoxyethyl)benzenes gradually convert into vinylarenes; (3) Cu-catalyzed amino-alkoxylation of the intermediary vinylarenes to yield arylethanolamines. This method introduces C-N and C-O bonds regioselectively at the homobenzylic and benzylic positions of ethylarenes.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yusuke Masuda, Daichi Ikeshita, Kosuke Higashida, Masaki Yoshida, Naoki Ishida, Masahiro Murakami, Masaya Sawamura
Summary: Under photocatalytic conditions, tri(t-butyl)phosphine and terminal alkynes undergo 1,2-phosphorus-migrative [3 + 2] cycloaddition in the presence of a proton source. The reaction shows broad functional group tolerance and yields substituted cyclic phosphonium salts that can be further derivatized by Wittig olefination. Theoretical studies suggest that the phosphorus 1,2-migration of a β-phosphonioalkyl radical proceeds through a phosphine radical cation-alkene complex as a pseudointermediate, with the two fragments in the intermediate bound to each other through multiple noncovalent interactions.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Keito Fuke, Tomoya Miura
Summary: This study reports a regioselective approach for the 1,2-hydro(cyanomethylation) of unactivated aliphatic alkenes. A cyanomethyl radical is added onto alkenes to form alkyl radicals, which then undergo further reactions to produce one-carbon-extended nitriles.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
