Article
Chemistry, Multidisciplinary
Yulin Han, Anni Qin, Qian Zhang, Xue Zhang, Hui Qian, Shengming Ma
Summary: The Rh-catalyzed reaction allows for the efficient synthesis of cis-fused bicyclic products with excellent selectivity and tolerance towards synthetically useful functional groups. The proposed mechanism involves the rapid racemization of the allene moiety in the starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Yujia Gao, Juan Zhang, Wenyu Shan, Weihong Fei, Jinzhong Yao, Weijun Yao
Summary: In this study, a trimerization reaction of gamma-aryl-3-butynoates was achieved through catalysis, leading to the formation of exocyclopentene derivatives with an allcarbon quaternary stereocenter. The reaction exhibited high stereoselectivity and enantioselectivity, delivering optically pure products with high enantiomeric excess values.
Article
Chemistry, Organic
Nengzhong Wang, Yimin Lang, Junjie Wang, Zugen Wu, Yixin Lu
Summary: A highly selective sequential annulation reaction using phosphine catalyst has been developed to construct multifunctional cis-fused bicyclic[3,3,0]octene scaffolds. The reaction involves the reaction between allenoates and arylidenemalononitriles and allows for the creation of three consecutive stereogenic centers, including one quaternary carbon center, in a one-step operation. The reported protocol is scalable, operates under mild conditions, and can be used to synthesize the core structural motifs of various natural products.
Article
Chemistry, Multidisciplinary
Ryota Shimotsukue, Kohei Fujii, Yu Sato, Yuki Nagashima, Ken Tanaka
Summary: We have developed a rhodium-catalyzed intermolecular [2+2+2] cycloaddition reaction with excellent selectivity, producing chiral cyclohexadienylamines. The reaction involves the reaction of two arylacetylenes with a cis-enamide or a silylacetylene to yield the desired products with complete regio- and diastereoselectivity and high yields and enantioselectivity. Mechanistic studies suggest the formation of a rhodacyclopentadiene intermediate from the terminal alkynes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Anni Qin, Qian Zhang, Hui Qian, Yulin Han, Shengming Ma
Summary: In this study, the first example of Rh-catalyzed kinetic resolution of 1,3-disubstituted allene-1,3-dienes involving intramolecular [4+2]-cycloaddition was developed. The reaction produced aza-[4.3.0]bicyclic compounds with high enantio- and E-selectivity, and the mechanism was elucidated through careful control experiments. The synthetic potentials of highly enantioenriched bicyclic products were also demonstrated.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Organic
Shabbir Ahmed Khan, A. Sanjeeva Kumar, K. C. Kumara Swamy
Summary: Under the catalysis of DABCO, pyridine, or tetra-n-butyl ammonium bromide (TBAB), the same 5-acetoxy allenoates and thioamides undergo different annulations to give dihydrothiophene, thiopyran, or thiazole motifs. Pyridine-catalyzed [3 + 2] annulation leads to essentially single diastereomers of dihydrothiophenes. In contrast, allenoates deliver thiopyran motifs in good to high yields through 6-exo-dig cyclization under DABCO catalysis. In the thiazole forming [3 + 2] annulation, tetra-n-butyl ammonium bromide (TBAB) facilitates addition-elimination and 5-exo-trig cyclization, resulting in thiazole cores exclusively with a Z-isomeric exocyclic double bond.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yu Sato, Masato Abekura, Tomohiro Oriki, Yuki Nagashima, Hidehiro Uekusa, Ken Tanaka
Summary: This study reports a Rh-catalyzed high-yielding and highly 1,3,5-selective room temperature [2+2+2] cycloaddition reaction for the synthesis of chemically stable aryl ether cages of various shapes and sizes. These aryl ether cages are highly crystalline and intertwine with each other to form regular packing structures. Some aryl ether cages encapsulated isolated water molecules in their hydrophobic cavity by hydrogen bonding with the multiple ester moieties.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Min Liu, Leijie Zhou, Wangyu Shi, Yimin Hu, Jianning Liao, Zeqing Duan, Wei Wang, Yongjun Wu, Bing Zheng, Hongchao Guo
Summary: The delta-sulfonamido-substituted enones were utilized as phosphine acceptors in the phosphine-catalyzed (4 + 2) annulation of 1,1-dicyanoalkenes. They acted as a four-membered synthon to react with 1,1-dicyanoalkenes under mild reaction conditions, producing piperidine derivatives in moderate to excellent yields with good to excellent diastereoselectivities.
Article
Chemistry, Multidisciplinary
Jingxiong Lai, You Huang
Summary: An unprecedented phosphine-catalyzed formal Buchner [6+1] annulation has been developed, providing a concise route to cycloheptatrienes by introducing an electrophilic allylic group. The reaction involves a [4+2] Diels-Alder reaction and ring expansion of the substrate structure.
CHEMICAL COMMUNICATIONS
(2023)
Article
Chemistry, Organic
Emanuele Azzi, Giovanni Ghigo, Lorenzo Sarasino, Stefano Parisotto, Riccardo Moro, Polyssena Renzi, Annamaria Deagostino
Summary: In this study, a photoinduced chloroamination cyclization of allenes was presented, resulting in the formation of 2-(1-chlorovinyl)pyrrolidines and related heterocycles. N-chlorosuccinimide (NCS) was used as the chlorine source. Detailed experimental and computational mechanistic studies revealed the formation of a common nitrogen centered radical (NCR) through multiple reaction pathways. The NCR then undergoes intramolecular cyclization and chlorination to yield the final product.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Physical
John M. Halford-McGuff, Alexandra M. Z. Slawin, Allan J. B. Watson
Summary: This article presents a predictive model for the reactivity and turnover of the Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and alkynes. Contrary to the proposed electronic model, this model suggests that the reaction is predominantly driven by steric effects, and turnover is proportional to alkyne steric parameters. The model allows for the prediction of catalyst loading, turnover, and reaction yield based on the assessment of the alkyne's steric parameter.
Article
Chemistry, Applied
Rayhane Hammami, Pascale Maldivi, Christian Philouze, Sebastien Carret, Benjamin Darses, Soufiane Touil, Jean-Francois Poisson
Summary: A variety of 4-phosphinylpyrrolidin-3-ones were synthesized via a [3+2] cycloaddition reaction between aryl aldonitrones and phosphinylallenes. The products were obtained as unique 4,5-trans diastereomers in yields ranging from 47% to 80% for 23 examples. Chiral racemic allenes exhibited a moderate 2:1 to 4:1 2,5-diastereoselectivity. Under the reaction conditions, the cycloadducts undergo a rearrangement to selectively afford the corresponding pyrrolidin-3-ones. DFT calculations provided insights into the mechanism involving the homolytic cleavage of the N-O bond of the cycloadduct.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Multidisciplinary
Hannah S. Slocumb, Shaozhen Nie, Vy M. Dong, Xiao-Hui Yang
Summary: This study demonstrates the first enantioselective hydroselenation of styrenes, accessing organoselenium building blocks with selectivity for the branched isomer. Through a Rh-hydride pathway, C-Se bonds can be formed with excellent regio- and enantiocontrol.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Organic
Qiuxia Jiang, Anquan Li, Xiang Liu, Yue Yu, Baofu Zhu, Hua Cao
Summary: An efficient and metal-free approach for synthesizing diverse functionalized furan derivatives using ene-yne-ketones and 1,3,5-triazinanes has been developed. This atom-economical and environment-friendly protocol allows for selective C-N and C-O bond formation in polysubstituted furans in a one-pot reaction.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
Leo Chaussy, Marion Delorme, Alexander Punter, Yannick Carissan, Jean-Luc Parrain, Muriel Amatore, Paola Nava, Laurent Commeiras
Summary: This study computationally and experimentally investigated the mechanism of cobalt cycloaddition reactions. Based on the nature of the reaction and the nature of the 2π partner, spiro-lactone and spiro-lactam complexes were successfully synthesized.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Organic
Tsuyoshi Mita, Hiroki Masutani, Sho Ishii, Yoshihiro Sato
Article
Chemistry, Multidisciplinary
Yoshihiro Oonishi, Shuichi Masusaki, Shunki Sakamoto, Yoshihiro Sato
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2019)
Article
Chemistry, Applied
Tsuyoshi Mita, Masashi Uchiyama, Yoshihiro Sato
ADVANCED SYNTHESIS & CATALYSIS
(2020)
Article
Chemistry, Organic
Toshiki Akiyama, Yuki Wada, Makito Yamada, Yasunori Shio, Tetsuo Honma, Shuhei Shimoda, Kazuki Tsuruta, Yusuke Tamenori, Hitoshi Haneoka, Takeyuki Suzuki, Kazuo Harada, Hayato Tsurugi, Kazushi Mashima, Jun-ya Hasegawa, Yoshihiro Sato, Mitsuhiro Arisawa
Article
Chemistry, Physical
Ryohei Doi, Koji Shimizu, Yuma Ikemoto, Masashi Uchiyama, Mikiko Koshiba, Atsushi Furukawa, Katsumi Maenaka, Satoshi Watanabe, Yoshihiro Sato
Summary: This study reports a nickel-catalyzed cascade reaction to construct a 3-acylbenzo[b]furan skeleton. Through reaction condition optimization, the catalyst loading could be reduced to 5-10 mol %, leading to the synthesis of various functionalized compounds. Stoichiometric study of nickel complexes and DFT calculations were conducted to support a possible reaction mechanism.
Article
Chemistry, Multidisciplinary
Ryohei Doi, Kanako Hayashi, Yoshihiro Sato
Summary: In this study, palladium-catalyzed decarboxylative alpha-polyfluoroarylation of ketones was reported. By screening reaction conditions, XPhos and Ruphos were selected as ancillary ligands for Pd(0) catalysts, enabling the reaction to be applied to various substrates. A cross-over experiment was conducted to gain insight into the reaction mechanism.
Article
Chemistry, Organic
Yoshihiro Oonishi, Shunki Sakamoto, Shuya Agata, Yoshihiro Sato
Summary: In the Rhodium(I)-catalyzed enantioselective cyclization of enynes, the presence of different functional groups on the substrate molecules affects the structure and yield of the products, with C(sp(3))-H bond activation being an important high energy barrier step in the cyclization reaction.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Organic
Souta Misawa, Asaki Miyairi, Yoshihiro Oonishi, Steven P. Nolan, Yoshihiro Sato
Summary: Polarized alkynes such as ynol ethers and ynamides undergo Au(I)-catalyzed hydroalkoxylation/Claisen rearrangement cascade reactions with allylic alcohols, proceeding under mild conditions with high regioselectivity. The resulting gamma,delta-unsaturated esters or amides are formed in an atom-economical manner using the [Au(IPr)NTf(2)] catalyst.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Applied
Yoshihiro Oonishi, Kazuki Takagishi, Yi-Min Liu, Yoshihiro Sato
Summary: This article describes the rhodium-catalyzed enantioselective hydroacylation of racemic alkynals with a substituent at the alpha-position of the carbonyl group. The reaction can be applied to a wide range of substrates (22 examples), and mechanistic studies reveal a dynamic kinetic resolution (DKR) process during the hydroacylation, leading to various cyclic ketones with yields of 47-93% and enantiomeric ratios (er) of 59:41 to 97:3 from racemic starting materials.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Koji Yamada, Kaho Ishizawa, Yoshihiro Oonishi, Yoshihiro Sato, Takahide Nishi
Summary: This study presents a practical synthetic method for accessing oxazolidinone-2,3-fused indoline and azaindoline derivatives through one-pot cyclization. These derivatives, which contain sp3-hybridized carbons, could serve as novel scaffolds in medicinal chemistry.
Article
Chemistry, Organic
Mikiko Koshiba, Yuto Furuki, Kazuhiro Morisaki, Ryohei Doi, Yoshihiro Sato
Summary: We report a nickel-catalyzed migratory cycloisomerization reaction for the synthesis of 2,3-disubstituted indoles. The reaction proceeds via acyl transfer on the nitrogen atom of the substrate to the C3 position in the product, and a suitable N-heterocyclic carbene ligand is used in the reaction.
ASIAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Yoshio Hato, Timothy F. Jamison
Summary: Efficient and robust synthesis of active pharmaceutical ingredients (APIs) requires the use of continuous flow chemistry. This study investigates continuous synthetic approaches to ondansetron, an essential medicine. Continuous condensation and Mannich reactions were established, along with a continuous work-up and purification process. A batch process was employed for an elimination and Michael addition step, showing the complementary advantages of flow and batch chemistry in API synthesis.
REACTION CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Organic
Asaki Miyairi, Yoshihiro Oonishi, Yoshihiro Sato
Summary: This study successfully demonstrated the one-pot synthesis of fully substituted 2-aminofurans via a gold-catalyzed cascade reaction, under highly mild conditions.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Ryohei Doi, Yoshihiro Sato
NICKEL CATALYSIS IN ORGANIC SYNTHESIS: METHODS AND REACTIONS
(2020)
Meeting Abstract
Chemistry, Multidisciplinary
Toshiki Akiyama, Tetsuo Honma, Kazuki Tsuruta, Yusuke Tamenori, Yohei Ueda, Hayato Tsurugi, Kenichi Murai, Ohno Shohei, Kazushi Mashima, Hiromichi Fujioka, Yoshihiro Sato, Mitsuhiro Arisawa
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY
(2019)
