Article
Chemistry, Organic
Timothy J. Paris, Chris Schwartz, Rachel Willand-Charnley
Summary: The successful synthesis and isolation of heteroaryl ketene acetals were achieved through intermolecular transfer of alkoxyl from electrophilic peroxides to lithiated benzofurans, indoles, and pyridines, showing enhanced reactivity towards electrophilic oxygen. The stability of the heteroaryl ketene acetals throughout purification techniques was superior, possibly due to increased aromaticity of the indole and pyridine structures. The reported products demonstrated resilience to workup and flash column chromatography procedures, overcoming typical issues associated with alkyl ketene acetal synthesis.
JOURNAL OF ORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yunhui Feng, Hang Luo, Fangnian Yu, Qian Liao, Luqing Lin
Summary: Here, we present a visible-light-promoted single nickel catalysis for achieving various C-N couplings of aryl chlorides/bromides and diverse N-nucleophiles using sodium iodide as the activator. The single nickel catalyst plays a dual role in halogen exchange and C-N coupling, which are crucial for obtaining the desired coupling products. This catalytic process eliminates the need for an exogenous photocatalyst and offers a sustainable and efficient approach for mild C-N coupling. Experimental studies, along with UV-vis and NMR analyses, demonstrate that the halogen exchange between both Ni-II and Ni-III-halide complexes and the iodide anion is a significant process in the formation of coupling products.
Article
Chemistry, Organic
Elliot H. E. Farrar, Matthew N. Grayson
Summary: A new reaction model relying on different interactions between the nucleophile, electrophile, and catalyst has been proposed to explain the selectivity in the oxazaborolidine-catalyzed Mukaiyama aldol reaction, as the current models based on hydrogen bonding alone are insufficient.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Zhuqing Liu, Jiang Lou, Jiaqi Xiao
Summary: A TBAI/K2S2O8-promoted [4 + 2] annulation of ketene N,S-acetals, and N-tosylhydrazones was efficiently developed, enabling straightforward access to a variety of trisubstituted pyridazines in reasonable to good yields. The synthetic methodology features a broad substrate scope and a good functional group tolerance. Control experiments demonstrated the indispensability of the alkylthio functionality in the enaminone substrates.
Article
Chemistry, Organic
Tianyu Zhang, Zhenkun Yang, Dapeng Zhou, Fuliang Meng, Zhengyu Han, Hai Huang
Summary: This work presents a new catalytic and highly chemoselective cross-Claisen condensation of esters, using silyl ketene acetals as carbonic nucleophiles. The process offers mild conditions and good functional group tolerance compared to traditional Claisen condensation.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Organic
Mingpan Yan, Longzhi Zhu, Xingxing Zhang, Shuang-Feng Yin, Nobuaki Kambe, Renhua Qiu
Summary: An efficient methodology for the synthesis of large sterically hindered triarylamines in a single step was developed, with good to excellent yields using inexpensive nickel catalyst. Various bromides and substituted 8-aminoquinolines can be tolerated in the reaction, and preliminary fluorescence results indicate potential in material chemistry for these sterically hindered and conjugated triarylamines.
Review
Chemistry, Multidisciplinary
Koji Hirano
Summary: The development of new C-N bond forming strategies is crucial due to the importance of nitrogen atom in bioactive molecules and functional materials. This account presents the nitrogen-umpolung-enabled copper-catalyzed highly selective amination protocols developed by the author's research group. The application of these methods to the synthesis of alkyl-amines with rich functionality is demonstrated.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2023)
Article
Chemistry, Multidisciplinary
Chenhao Zhang, Anthony Z. Gao, Xin Nie, Chen-Xi Ye, Sergei I. Ivlev, Shuming Chen, Eric Meggers
Summary: This study demonstrates the catalytic deracemization of ketones with alpha-stereocenters in a single reaction through photoredox deprotonation and enantioselective protonation. By utilizing a photoredox catalyst and a tertiary amine, nonracemic carbonyl compounds with up to 97% enantiomeric excess can be obtained. This light-driven strategy provides a blueprint for deracemizations of common carbonyl compounds.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Organic
Zheng-Hai Wang, Dong-Hui Wang
Summary: A Cu-catalyzed straightforward synthesis of benzoxazoles from free phenols and cyclic oxime esters is reported, with moderate to good yields under mild reaction conditions. Large-scale syntheses of Ezutromid and Flunoxaprofe are demonstrated in one or two steps. The proposed catalytic mechanism involves Cu-catalyzed amination via inner-sphere electron transfer and consequent annulation.
Article
Chemistry, Organic
Shrikant M. Ghodse, Navnath T. Hatvate, Vikas N. Telvekar
Summary: A simple and efficient method using aqueous sodium dichloroiodate has been established for the synthesis of alpha-heteroaryl ketones from aryl ketones and amine. This method is mild, operationally simple, with a short reaction time, and yields moderate to good amounts of alpha-N-heteroaryl ketone derivatives.
JOURNAL OF HETEROCYCLIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Ryan T. McGuire, Arun A. Yadav, Mark Stradiotto
Summary: The report presents the first Ni-catalyzed N-arylation of beta-fluoroalkylamines with broad scope. The use of a stable pre-catalyst allows for reactions to be conducted at room temperature or using a commercially available dual-base system, providing a mild protocol with broad substrate scope and enantioselective transformations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Organic
Sheng Zhang, Ziyang Wang, Ya Gao, Masahiko Yamaguchi, Ming Bao
Summary: This article describes the first palladium-catalyzed remote C-H dimethylamination of 1-chloromethylnaphthalenes using N,N-dimethylformamide as the dimethylamino source. The dimethylamination occurred exclusively at the 4-position of 1-chloromethylnaphthalenes in 2-methyltetrahydrofuran under mild conditions, resulting in good to high yields of 1-(N,N-dimethylamino)-4-alkylnaphthalenes. The halogen atom remained intact during the dimethylamination process. A conveniently synthesized and successfully utilized P,N bidentate ligand was employed in the Kumada-Corriu reaction.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Lin Feng, Jiaxin Yao, Lin Yu, Wengui Duan
Summary: We have developed an efficient palladium-catalyzed denitrative N-arylation method, which enables the cross-coupling of N-H heteroarenes with nitroarenes. This method allows for the selective synthesis of various functionalized N-arylated heterocycles with moderate to excellent yields. Furthermore, its success in scale-up experiments and late-stage modification of natural products and pharmaceutical derivatives demonstrates the synthetic potential of this direct denitrative N-arylation protocol in synthetic chemistry.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Organic
Hangcheng Ni, Chaoming Li, Xingzi Shi, Xianyue Hu, Hui Mao
Summary: The combination of ligand-to-metal charge transfer radical chemistry and metal catalysis enables visible-light-promoted N-H alkylation of amides and N-heterocycles, producing a wide variety of N-alkylated products. The applicability of this method is further demonstrated through late-stage alkylation of N-H-containing pharmaceuticals. A mechanistic study reveals the key role of hydrogen atom transfer in activating C(sp(3))-H precursors.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Dongming Zhang, Bin Lv, Pan Gao, Xiaodong Jia, Yu Yuan
Summary: An efficient Cu-catalyzed strategy for the direct C–H amination of arenes in high yields using N-hydroxyphthalimide as the amidyl radical precursor under air is reported. A possible mechanism is proposed that proceeds via a radical reaction in the presence of CuBr and triethyl phosphite.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
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
Tomoya Miura, Kohei Hagiwara, Takayuki Nakamuro, Yuuya Nagata, Naoki Oku, Masahiro Murakami
Summary: A method for the synthesis of 3,5-disubstituted-1,2,4-triazoles from nitriles and 5-aryltetrazoles is described. The reaction involves ring-chain tautomerization, denitrogenation, and 1,3-dipolar cycloaddition to achieve regioselective formation of the desired triazoles.
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, 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
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)
