Article
Chemistry, Physical
Jihoon Moon, Takusho Kin, Karin Mizuno, Shuji Akai, Kyohei Kanomata
Summary: This study presents a chemoenzymatic dynamic kinetic resolution (DKR) of racemic sec-alcohols using immobilized lipase and aqueous sulfuric acid as catalysts for kinetic resolution and racemization, respectively. The use of nanoparticle-stabilized phase separation in a Pickering emulsion allowed the use of these incompatible catalysts in a single vessel. The racemization reaction in the aqueous sulfuric acid solution effectively suppressed side reactions, resulting in high yields and optical purities.
Article
Chemistry, Multidisciplinary
Jose A. Carmona, Patricia Rodriguez-Salamanca, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An atroposelective Ir-catalyzed dynamic kinetic resolution (DKR) of 2-(quinolin-8-yl)benzaldehydes/1-naphthaldehydes is achieved by transfer hydrogenative coupling of allyl acetate. The reaction leads to the installation of central and axial chirality, with high diastereoselectivities and excellent enantioselectivities when ortho-cyclometalated iridium-DM-BINAP is used as the catalyst. The racemization of the substrates is facilitated through a designed transient Lewis acid-base interaction between the quinoline nitrogen atom and the aldehyde carbonyl group.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Organic
Bo Ding, Qilin Xue, Shihu Jia, Hong-Gang Cheng, Qianghui Zhou
Summary: This review provides an overview of recent advances in catalytic nonenzymatic kinetic resolution (KR) of tertiary alcohols, including organocatalysis and metal catalysis.
SYNTHESIS-STUTTGART
(2022)
Review
Chemistry, Organic
Helene Pellissier
Summary: Organocatalytic dynamic kinetic resolution (DKR) has emerged as a promising field in the past two decades, allowing efficient separation of chiral compounds. This review aims to provide an update on organocatalytic DKRs since 2016.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Yifan Feng, Ruixuan Shi, Mingfang Yang, Yunlong Zheng, Zhenjie Zhang, Yao Chen
Summary: By utilizing the dissociation equilibrium of metal-organic frameworks (MOFs) mediated by enzymes, a dynamic defect generation strategy for enzyme immobilization is created to overcome the current challenges. Enzymes can compete with original ligands and generate defects by releasing metal clusters of MOFs, allowing for the gradual transport of enzymes from the surface to inside. Various enzymes can be efficiently immobilized in MOFs to create composites with good enzymatic activities, protective performances, and exceptional reusabilities. In addition, multienzyme bioreactors capable of efficient cascade reactions can be generated. This study provides new opportunities for constructing highly efficient biocatalysts incorporating different types of enzymes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Mengyao Tang, Huanchao Gu, Shunlong He, Subramani Rajkumar, Xiaoyu Yang
Summary: An efficient protocol for kinetic resolution of tertiary alcohols has been developed via unprecedented asymmetric enamide-imine tautomerism process enabled by chiral phosphoric acid catalysis. This method is particularly effective for a series of 1,1-dialkyl substituted allyl alcohols, producing chiral tertiary alcohols that are difficult to access through other asymmetric methods. Facile and versatile transformations of the chiral products demonstrate the value of this kinetic resolution method.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Organic
Chen Yunrong, Liu Wei, Yang Xiaoyu
Summary: Chiral tertiary alcohols play important roles in various bioactive compounds, and significant progress has been made in the nonenzymatic kinetic resolution of tertiary alcohols in recent years, exploring the application of novel asymmetric reactions and catalytic systems.
CHINESE JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Minghui Zhu, Qinglong Zhang, Weiwei Zi
Summary: The study presents a dual-metal catalyzed diastereodivergent coupling method for the synthesis of beta-amino alcohols with multiple stereoisomers, enabling the concise preparation of natural products such as mycestericins F and G.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jan Seliger, Martin Oestreich
Summary: A novel approach for the dynamic kinetic resolution of benzylic alcohols was reported, achieving enantioselective silylation of racemic alcohol mixtures in high yields by merging different catalytic processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Ming-Sheng Xie, Ning Li, Yin Tian, Xiao-Xia Wu, Yun Deng, Gui-Rong Qu, Hai-Ming Guo
Summary: A study reported the use of bifunctional chiral PPY N-oxides as catalysts for dynamic kinetic resolution of racemic carboxylic esters, achieving high yields and enantioselectivity for the synthesis of chiral alpha-aryl alpha-alkyl carboxylic esters. Mechanistic studies revealed the crucial role of oxygen atoms in PPY N-oxides during the reaction process.
Article
Chemistry, Applied
Yongkai Pan, Qianwen Jiang, Subramani Rajkumar, Chaofan Zhu, Jinglei Xie, Shaoze Yu, Yunrong Chen, Yu-Peng He, Xiaoyu Yang
Summary: A series of cyclohexyl-fused SPINOL-derived phosphoric acids have been developed for the kinetic resolution of 2-N-acylamido tertiary allylic alcohols, providing access to chiral oxazolines with high enantioselectivities. Gram-scale reactions with 1 mol% catalyst loading and transformations of the chiral products demonstrate the value of these methods.
ADVANCED SYNTHESIS & CATALYSIS
(2021)
Article
Chemistry, Multidisciplinary
Chenghua Deng, Bai-Qiao Song, Matteo Lusi, Andrey A. Bezrukov, Molly M. Haskins, Mei-Yan Gao, Yun-Lei Peng, Jian-Gong Ma, Peng Cheng, Soumya Mukherjee, Michael J. J. Zaworotko
Summary: A new chiral metal-organic material, CMOM-5, has been developed to design chiral crystalline sponges and determine the crystal structures of liquid enantiomers. CMOMs can mimic the enantioselectivity of biomolecules and can be fine-tuned for structure and properties. CMOM-5, composed of rod building blocks and bipy linkers, can adapt its pore structure to bind different guest molecules, exhibiting chiral resolution with high enantiomeric excess values. The flexibility of CMOM-5 allows the determination of eight enantiomeric crystal structures, including the first crystal structures of R-4P2B, S-4P2B, and R-MPE ambient liquids.
CRYSTAL GROWTH & DESIGN
(2023)
Article
Chemistry, Physical
Patricia Rodriguez-Salamanca, Gonzalo de Gonzalo, Jose A. Carmona, Joaquin Lopez-Serrano, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: This article describes a highly enantioselective biocatalytic dynamic kinetic resolution (DKR) for configurationally labile N-arylindole aldehydes. The DKR is achieved through atroposelective bioreduction of the carbonyl group using commercial ketoreductases (KREDs), resulting in axially chiral N-arylindole aminoalcohols with excellent conversions and optical purities. The strategy relies on the racemization of the stereogenic axis facilitated by a transient Lewis pair interaction between NMe2 and the aldehyde groups. This protocol offers a broad substrate scope under mild conditions.
Article
Chemistry, Multidisciplinary
Linlong Dai, Yuheng Liu, Qing Xu, Meifang Wang, Qiaohong Zhu, Peiyuan Yu, Guofu Zhong, Xiaofei Zeng
Summary: This paper presents a dynamic kinetic resolution method for the synthesis of axially chiral diaryl ethers. By using a Bronsted acid catalyzed atroposelective transfer hydrogenation (ATH) reaction, the desired diaryl ethers could be obtained in moderate to good chemical yields (up to 79%) and high enantioselectivities (up to 95% ee) under standard reaction conditions. These structural motifs are interesting precursors for further transformations and may have potential applications in the synthesis of chiral ligands or catalysts.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Faju Li, Linhong Long, Yan-Mei He, Zeyu Li, Hui Chen, Qing-Hua Fan
Summary: A unique family of chiral macrocyclic ligands with a tunable saddle-shaped cavity is described. Using their manganese(I) complexes, the first example of earth-abundant transition metal-catalyzed asymmetric formal anti-Markovnikov hydroamination of allylic alcohols was achieved, providing a practical access to synthetically important chiral gamma-amino alcohols. The study revealed the remarkable role of the macrocyclic framework in the reaction process.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)