Article
Chemistry, Multidisciplinary
Wenpeng Ma, Li-Chuan Liu, Kun An, Tao He, Wei He
Summary: A Rh-catalyzed desymmetrization of dihydrosilanes under simple and mild conditions provides easy access to a range of chiral monohydrosilanes with good yields and excellent enantioselectivities (up to >99% ee). These monohydrosilanes serve as a useful platform to access stereogenic silicon compounds and probe silicon stereochemistry.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Dawson J. Konowalchuk, Dennis G. Hall
Summary: In this study, a divergent synthetic strategy was developed to transform an optically enriched scaffold into a variety of derivatives with different substitution patterns through desymmetrization and cross-coupling reactions. This method exhibits high yields and enantioselectivity, and can be applied to the synthesis of valuable tetra-C-substituted cyclobutane products.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Kai Dong, Chen Xu, Jinsong Ren, Xiaogang Qu
Summary: Nanozymes, which combine enzymatic activity and nanomaterials, have gained significant attention. However, substrate selectivity is often overlooked in the development of nanozymes. This Mini-review provides an overview of recent advances in synthesizing chiral nanozymes and their enantioselective biological catalysis, along with current challenges, potential solutions, and future trends.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Ryoji Sugiyama, Masahisa Nakada
Summary: A highly enantio- and diastereoselective Mukaiyama-Michael reaction using an enol silane of tert-butyl thiopropionate is described. The yield, diastereomer ratio, and enantiomeric excess were 87%, 27:1, and 91% ee under stoichiometric conditions, while under catalytic conditions, they were 89%, 49:1, and 88% ee, respectively. The highly stereoselective epimerization of the Mukaiyama-Michael reaction product is also described, yielding the product with a 77% yield and a diastereomer ratio of 22:1. A method for synthesizing all four stereoisomers of the product as useful chiral building blocks has been established due to the availability of both enantiomers of the ligand for this reaction.
Article
Chemistry, Multidisciplinary
Ekaterina Lerman, Shlomo Levinger, Amnon Albeck
Summary: The study developed a method for synthesizing optically active C-terminal building blocks and expanded it to building blocks with side chains functionalized with oxygen, nitrogen, or halogen. The key step is the enzymatic hydrolysis introducing optical activity, while the ordering of subsequent chemical reactions will determine the absolute stereochemistry of the final building blocks.
Article
Chemistry, Organic
Si Zhang, Ruo-Shi Jin, Yan-Fei Niu, Xing -Ping Zeng
Summary: A one-pot catalytic asymmetric approach to chiral quaternary-carbon-containing cyclobutanone-fused 4-aminoquinoline derivatives is presented. This process involves a chiral phosphoric acid-catalyzed desymmetric condensation of cyclobutane-1,3-diones with 2-halogenated anilines and a Pd-catalyzed coupling of the chiral enaminone intermediates with isocyanides. The reactions provide good to high yields and enantioselectivities, with up to 97% ee achieved.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Remi Jouhannet, Samuel Dagorne, Aurelien Blanc, Pierre de Fremont
Summary: This article summarizes the synthesis and applications of well-defined gold(III) complexes reported over the last fifteen years, exploring the applications of gold catalysis in organic chemistry and the potential of gold(III) complexes in pharmacology.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Min Zhu, Martin Oestreich
Summary: A group-selective monosilylation of silanediols using List's counteranion-directed silylation methodology is described. The enantioselectivity is achieved by generating a silylium-ion-like silicon electrophile from an allylic silane paired with an imidodiphosphorimidate (IDPi), enabling discrimination of the two hydroxy groups attached to the prochiral silicon atom. Furthermore, the enantioselectivity is improved by a subsequent kinetic resolution, resulting in silicon-stereogenic disiloxanes with high enantiocontrol.
Article
Chemistry, Multidisciplinary
Linghua Wang, Tao Li, Saima Perveen, Shuai Zhang, Xicheng Wang, Yizhao Ouyang, Pengfei Li
Summary: A nickel-catalyzed general, efficient, and highly enantioselective carboxylation reaction of racemic benzylic (pseudo)halides has been developed, utilizing atmospheric CO2 under mild conditions. A unique chiral 2,2'-bipyridine ligand enabled both high reactivity and stereoselectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Applied
Raja K. K. Rit, Hongyi Li, Stephen P. P. Argent, Katherine M. M. Wheelhouse, Simon Woodward, Hon Wai Lam
Summary: Chiral dienes are important ligands in asymmetric catalysis but they are difficult to obtain. In this study, a simple chiral allenecarboxanilide was used to produce pseudoenantiomeric bicyclo[2.2.2]octa-2,5-dienes containing an alkenyl bromide via intramolecular [4+2] cycloaddition. These compounds can be easily functionalized to provide diverse chiral diene ligands. The synthesis is straightforward and can be conducted on a large scale. The resulting ligands exhibit high performance in nine types of enantioselective Rh(I)-catalyzed addition reactions.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Review
Chemistry, Physical
You-Dong Shao, Dao-Juan Cheng
Summary: Chiral phosphoric acid catalysis has witnessed significant development in the past two decades, with successful attempts in synthesizing enantioenriched axially chiral compounds through various strategies. This review highlights the advances in atropisomeric heterocycles construction enabled by chiral phosphoric acid catalysis, aiming to motivate continuous interest in atroposelective reactions.
Article
Multidisciplinary Sciences
Zhihua Cheng, Matthew R. Jones
Summary: The study reports the self-assembly of 2D chiral superlattices from achiral tetrahedron-shaped building blocks, explains the formation mechanism, and lays the scientific foundation for the high-throughput assembly of planar chiral metamaterials.
NATURE COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Biki Ghosh, Mahesh Singh Harariya, Santanu Mukherjee
Summary: The desymmetrization approach enables the construction of centrally chiral unfunctionalized arenes from unsymmetrically substituted arene rings. This approach is based on a [4+2]-cycloaddition reaction and greatly simplifies the synthesis of chiral arenes with outstanding enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Dong-Huang Chen, Wei-Ting Sun, Cheng-Jie Zhu, Guang-Sheng Lu, Dong-Ping Wu, Ai-E Wang, Pei-Qiang Huang
Summary: The combination of transition-metal catalysis and organocatalysis has enabled chemists to achieve direct enantioselective reductive cyanation and phosphonylation of secondary amides, synthesizing enantioenriched chiral alpha-aminonitriles and alpha-aminophosphonates for the first time. The protocol is efficient, enantioselective, scalable, and the thiourea catalyst can be recycled and reused.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Shi-Jiang He, Shuai Zhu, Sheng-Qi Qiu, Wei-Yi Ding, Jun Kee Cheng, Shao-Hua Xiang, Bin Tan
Summary: This study discovered a novel type of axially chiral anthrone-derived skeleton by introducing axial chirality on symmetric anthrone skeletons through stereoselective condensation. The enantioenriched anthrones could be further transformed into dibenzo-fused seven-membered N-heterocycles with well-defined stereogenic center via Beckmann rearrangement.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Masami Sakamoto, Naohiro Uemura, Rei Saito, Haruna Shimobayashi, Yasushi Yoshida, Takashi Mino, Takashige Omatsu
Summary: Chiral symmetry breaking and asymmetric transformation were achieved by using optical vortices, with crystal nucleation controlled by the winding direction of the chiral optical vortices. This novel methodology combines enantioselective crystal nucleation with crystallization-induced dynamic optical resolution for amplifying molecular chirality.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Aoi Washio, Momoka Hosaka, Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
Summary: The highly enantioselective synthesis of p-anisoin was achieved through the benzoin condensation reaction using chiral NHC catalysts. The deracemization of racemic p-anisoin was efficiently performed by Viedma ripening under basic conditions. The handedness control of enantioselective crystallization could be achieved through the coexistence of optically active valine, due to the asymmetric transformation of p-anisoin with enantiomeric valine in the mother liquor.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Applied
Yasushi Yoshida, Tappei Fujimura, Takashi Mino, Masami Sakamotoa
Summary: This study reports an asymmetric synthesis method of chiral N,S-acetals using a chiral iodonium salt catalyst under neutral conditions, with good-to-excellent yields and enantioselectivities. The reaction mechanism and catalyst activation were studied through NMR experiments and DFT calculations, and the abnormal counteranion effect was also investigated.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Takumi Nakamura, Kazuma Ban, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
Summary: The study achieved asymmetric synthesis through photochemical reaction and crystallization-induced dynamic deracemization, demonstrating high enantioselectivity. Efficient deracemization was found achievable in the presence of a catalytic base in acetone under suitable conditions. Additionally, Viedma ripening technique can transform racemic indoline crystals into enantiomeric crystals with high enantioselectivity.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Kazutaka Sanada, Aoi Washio, Kazuki Nishihata, Fumitoshi Yagishita, Yasushi Yoshida, Takashi Mino, Shinichi Suzuki, Yoshio Kasashima, Masami Sakamoto
Summary: Chiral symmetry breaking of 3-phenylsuccinimides was achieved through crystallization-induced dynamic deracemization. Both N-propyl and N-(3-methoxyphenyl)-3-phenylsuccinimides crystallized as racemic conglomerates, with their crystal structures determined by single-crystal X-ray structure analysis. Rapid racemization via enolate ions under basic conditions was confirmed, while attrition-enhanced deracemization (Viedma ripening) on a larger scale resulted in enantiomeric crystals with >99% ee.
CRYSTAL GROWTH & DESIGN
(2021)
Article
Chemistry, Physical
Yasushi Yoshida, Takashi Mino, Masami Sakamoto
Summary: This study reports the design and development of chiral cyclic diarylbromonium salts, enabling highly selective Lewis acid XB catalysis with products reaching up to 96% ee.
Article
Chemistry, Multidisciplinary
Takumi Nakamura, Hiroki Ishikawa, Kazuma Ban, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
Summary: Atroposelective resolution of axially chiral nicotinamides was achieved through dynamic chiral salt formation with L-DBTA. Six types of nicotinamides that could not be optically resolved by preferential crystallization were studied. The kinetic analysis showed that the chiral conformation was retained for a significant period of time. Two methods of crystallization-induced asymmetric transformation, solvent evaporation and attrition-enhanced asymmetric transformation, were examined. The attrition method proved to be more effective for asymmetric amplification of diastereomeric salts of axially chiral materials.
Article
Chemistry, Applied
Isami Nakajima, Minori Shimizu, Yuta Okuda, Ryo Akiyama, Ryu Tadano, Masahiro Nagaoka, Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Hiraku Shinozaki, Tetsuya Yamamoto
Summary: In this study, a specific complex was synthesized and used as a catalyst to achieve the 1,2-addition reactions of organoboron compounds under base-free conditions.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Kazutaka Sanada, Aoi Washio, Hiroki Ishikawa, Yasushi Yoshida, Takashi Mino, Masami Sakamoto
Summary: This article presents a method for chiral symmetry breaking of monoacylated meso diols and demonstrates its effectiveness through experiments and structural analysis. The results show that Viedma ripening can efficiently produce enantiomer crystals, achieving asymmetric expression and amplification of sugar derivatives without an external chemical chiral source. Additionally, the method is successfully applied to asymmetric desymmetrization of acyclic meso-1,2-diols.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Takashi Mino, Toshiki Yamaoka, Kohei Watanabe, Chihiro Masuda, Shohei Kasano, Yasushi Yoshida, Ryo Takita, Yoshio Kasashima, Masami Sakamoto
Summary: P,olefin ligand/palladium catalyst systems can easily afford the corresponding 2-substituted 3-allylindole derivatives in good to excellent yields.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Norika Miyazaki, Kazutaka Sanada, Takumi Nakamura, Aoi Washio, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
Summary: The asymmetric amplification of p-anisoin was achieved using chiral amino acids as catalysts. Under basic conditions, p-anisoin crystallized as a conglomerate and underwent efficient deracemization through Viedma ripening. The chiral selectivity of the crystallization could be controlled by the coexistence of specific amino acids. L-amino acids favored the formation of (R)-anisoin crystals, while D-amino acids favored the formation of (S)-isomer crystals. This asymmetric transformation was attributed to the presence of enantiomeric amino acids in the mother liquor. Similar asymmetric transformations were observed in alpha-hydroxyketones such as acetoin.
CRYSTAL GROWTH & DESIGN
(2022)
Article
Biochemistry & Molecular Biology
Yasushi Yoshida, Tatsuya Ao, Takashi Mino, Masami Sakamoto
Summary: In this study, chiral halonium salts with an N-nitrosamine moiety were developed and applied to the Mannich reaction. The novel bromonium salt catalyst showed high yields and up to 80% ee. This is the first catalytic application of N-nitrosamines.
Article
Chemistry, Organic
Takashi Mino, Kaho Takaya, Kaito Koki, Natsume Akimoto, Yasushi Yoshida, Yoshio Kasashima, Masami Sakamoto
Summary: We synthesized N-alkyl-N-cinnamoyl amide type phosphine-olefin compounds 1 and observed axial chirality in the C(aryl)-N(amide) bond of compounds 1 using HPLC analysis with a chiral stationary phase column. Enantiomeric isomers of 1 were obtained and (-)-1 was demonstrated as a chiral ligand in Pd-catalyzed asymmetric allylic substitution reactions, leading to high enantioselectivity (up to 97% ee) in the esterification process.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Nobuo Yasuike, Chihiro Kachi-Terajima, Amir Karin, Takashi Mino, G. Andrew Woolley
Summary: Thiol-reactive reagents cannot be used for the modification of intracellular targets due to the presence of high concentrations of glutathione. This study proposes an equilibrium, entropic strategy using a cyanoacrylate-based thiol-reactive cross-linker to achieve target selectivity. The cross-linker shows high selectivity for reaction with target peptides and proteins containing paired thiols.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yasushi Yoshida, Seitaro Ishikawa, Takashi Mino, Masami Sakamoto
Summary: Novel, stable bromonium salts have been synthesized and utilized for the first time as catalysts in the Michael reaction, achieving excellent product yield (up to 96%).
CHEMICAL COMMUNICATIONS
(2021)
