Letter
Chemistry, Organic
Matthew C. Leech, Dmitrii Nagornii, Jamie M. Walsh, Cyrille Kiaku, Darren L. Poole, Joseph Mason, Iain C. A. Goodall, Perry Devo, Kevin Lam
Summary: A practical electrochemical method for the synthesis of tertiary hindered alkyl fluorides from carboxylic acids is developed, which is rapid, safe, and mild without the need for hydrofluoric acid salts or non-glass reactors. Collidinium tetrafluoroborate acts as both the supporting electrolyte and fluoride donor in this anodic fluorination. The compatibility of a wide range of functional groups and the potential for scale-up using flow electrochemistry are demonstrated.
Article
Chemistry, Organic
Jan Eric Neuburger, Alina Gazizova, Sven Tiedemann, Jan von Langermann
Summary: This study demonstrates a straightforward synthesis process to prepare substituted 1,2-amino alcohols from readily available aromatic methyl ketones. The reaction involves bromination, hydrolysis, and enzymatic conversion, resulting in a high yield and excellent enantiomeric excess. Interestingly, a keto-enol-tautomerism reaction leads to an unexpected isomer of the amino alcohol.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Chengdong Lv, Guangqiang Xu, Rulin Yang, Li Zhou, Qinggang Wang
Summary: The asymmetric kinetic resolution polymerization catalyzed by chiral phosphoric acid can produce stereogradient polycaprolactones with controlled properties such as chain-end fidelity, molecular weights, and molar mass dispersity. The resulting PCLs exhibit high quality thermal properties, viscoelasticity, and degradation characteristics.
Article
Chemistry, Organic
Jianhui Qiao, Wenju Chang, Wenxuan Zhao, Yong Liang, Shaozhong Wang
Summary: A kinetic resolution method has been developed for racemic spiroindolines with s factors <= 15200, allowing the access to enantiomerically enriched indoleannulated medium-sized lactams and spiroindolines through Ir-catalyzed asymmetric allylative ring-opening reaction. Density functional theory calculations support the accurate discrimination of two spiroindoline enantiomers by (eta(3)-allyl)-iridium(III) species and ensure the stereoselective formation of two contiguous stereogenic centers and one axis in the medium-sized lactams.
Article
Chemistry, Applied
Ken Okuno, Bun Chan, Seiji Shirakawa
Summary: Catalytic kinetic resolution is a reliable method for enantioselective synthesis of chiral molecules. However, it is challenging to perform kinetic resolution on racemic compounds with similar substituents at a chiral center. In this study, a kinetic resolution of a-allyl-a-propargyl carboxylic acids was achieved using a chiral bifunctional sulfide catalyst. The utility of the resulting optically active compounds was also demonstrated.
ADVANCED SYNTHESIS & CATALYSIS
(2023)
Article
Chemistry, Organic
Baixue Liu, Peng Liu, Xue Wang, Feng Feng, Zhen Wang, Wenqiang Yang
Summary: A general method for the gram-scale enantioselective synthesis of P-stereogenic cyclic phosphine oxides has been developed using copper-catalyzed dynamic kinetic resolution, leading to high yields and high enantioselectivities. The resulting products can be easily reduced to obtain useful P(III)-stereogenic cyclic phosphines. A proposed mechanism involves the unusual rapid racemization of SPOs.
Review
Chemistry, Applied
Li-Cheng Yang, Heping Deng, Hans Renata
Summary: This article summarizes the chemoenzymatic and biocatalytic methodologies for DKR developed in the past decade, highlighting their applications in the preparation of active pharmaceutical ingredients and emerging paradigms.
ORGANIC PROCESS RESEARCH & DEVELOPMENT
(2022)
Article
Chemistry, Multidisciplinary
Pengqian Luan, Yunting Liu, Yongxing Li, Ran Chen, Chen Huang, Jing Gao, Frank Hollmann, Yanjun Jiang
Summary: An aqueous chemoenzymatic cascade reaction was developed for enantioselective synthesis of tertiary alpha-aryl cycloketones, combining Pd-catalyzed C-C formation with enzymatic C=C asymmetric hydrogenation. The enzyme's stereopreference in AH of alpha-aryl cyclohexenones was studied, and an enantiocomplementary enzyme was obtained through site-directed mutation.
Article
Chemistry, Organic
Bin He, Jingyuan Song, Congcong Yin, Gen-Qiang Chen, Xumu Zhang
Summary: Asymmetric hydrogenation of aryldibenzylamino ketones catalyzed by the Ir/f-phamidol system was achieved through dynamic kinetic resolution, producing chiral compounds with high selectivity. This method offers excellent conversion and enantioselectivity, making it applicable in the synthesis of drug candidates and chiral ligands.
ORGANIC CHEMISTRY FRONTIERS
(2022)
Article
Chemistry, Multidisciplinary
Shang Gao, Jiaming Liu, Ming Chen
Summary: The study successfully synthesized compounds with high optical purity through catalytic asymmetric reactions, including (Z)-delta-hydroxymethyl-anti-homoallylic alcohols and alpha,beta-unsaturated aldehydes. Enantioconvergent pathways were utilized to achieve excellent optical purity.
Article
Chemistry, Organic
Taichiro Touge, Hideki Nara, Michio Kida, Kazuhiko Matsumura, Yoshihito Kayaki
Summary: Efficient dynamic kinetic resolution of cyclic halohydrins was achieved by asymmetric transfer hydrogenation of racemic alpha-haloketones using bifunctional oxo-tethered Ru(II) catalysts. The catalyst could produce chiral alcohols with various functional groups with excellent diastereo- and enantioselectivities, providing a concise synthetic approach to a dopamine D3 receptor ligand, (+)-PHNO.
Article
Chemistry, Organic
Ying Xiong, Han Lin, Chang-Liang Zhu, Yong-Hong Chen, Rong Ye, Guan-Wen Hu, Jian-Hua Xie, Qi-Lin Zhou
Summary: An efficient asymmetric hydrogenation via dynamic kinetic resolution was reported for the synthesis of chiral 2-arylcyclopentanols from a variety of racemic alpha-aryl-beta-ethoxycarbonyl cyclopentanones. The method, catalyzed by a chiral iridium Ir-SpiroPAP catalyst, showed high yields and excellent enantio- and diastereoselectivities, making it applicable for the synthesis of diverse chiral products.
Article
Chemistry, Multidisciplinary
Ken Okuno, Mana Hiraki, Bun Chan, Seiji Shirakawa
Summary: This article reports a method for the kinetic resolution of α-quaternary carboxylic acids through the bromolactonization of alkynes catalyzed by a chiral sulfide. This method provides a solution to the challenging task of separating α-quaternary carboxylic acids and shows promising results.
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN
(2022)
Article
Chemistry, Multidisciplinary
Minh Do, Stella I. Anosike, Timothy K. Beng
Summary: An intrinsic goal in synthetic methodology design is to find approaches that can convert readily accessible precursors into various products to tap into new 3D chemical space. In this study, readily available bicyclic lactam-bromolactones were analyzed in several fragment growth protocols, utilizing the halogen and lactone motifs as versatile linchpins for strategic bond construction.
Article
Chemistry, Organic
Grysette Daher, Gustavo Seoane
Summary: A set of linear and cyclic oligomers were synthesized from a suitable azido-alkyne monomer through click oligomerization. The optimization of the click reaction was achieved using dimerization as a model reaction. The product distribution of the oligomerization could be controlled by the monomer concentration and the use of additives, resulting in mainly cyclic oligomers consisting of tetramers, pentamers, and hexamers.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2022)
