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)
Review
Chemistry, Multidisciplinary
Lucy A. Harwood, Luet L. Wong, Jeremy Robertson
Summary: Kinetic resolution using biocatalysis is an excellent complementary technique to traditional asymmetric catalysis, producing valuable oxygenated structures for synthetic route development. Enzymes catalyzing the insertion of an oxygen atom into the substrate, such as the Baeyer-Villiger rearrangement, epoxidation, and hydroxylation, play a key role in oxidative kinetic resolution. These key enantiomer-enriched intermediates have important applications in natural product synthesis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
Fuzhuo Li, Li-Cheng Yang, Jingyang Zhang, Jason S. Chen, Hans Renata
Summary: A highly diastereo- and enantioselective biocatalytic transamination method was developed for the preparation of a broad range of aromatic beta-branched alpha-amino acids. The transformation proceeds through dynamic kinetic resolution unique to the optimal enzyme, showcasing its utility for the synthesis of sp(3)-rich cyclic fragments and total synthesis of jomthonic acid A.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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.
Review
Biotechnology & Applied Microbiology
Chenming Huang, Junling Liu, Jiali Fang, Xian Jia, Zhendong Zheng, Song You, Bin Qin
Summary: This review discusses the advances in the research area of KRED-catalyzed asymmetric synthesis for biomanufacturing of chiral chemicals with at least two chiral centers through the kinetic resolution (KR) approach and the dynamic kinetic resolution (DKR) approach.
FRONTIERS IN BIOENGINEERING AND BIOTECHNOLOGY
(2022)
Article
Chemistry, Organic
Donghui Guo, Qiupeng Peng, Bei Zhang, Jian Wang
Summary: The novel method described in this report allows for the atroposelective generation of axially chiral amino esters using hemiaminals formed in situ, with a wide substrate scope, good functional group tolerance, and rapid assembly of axially chiral amino esters with high enantioselectivities in good to high yields.
Article
Chemistry, Physical
Fang-Rui Zhang, Nan-Wei Wan, Jin-Mei Ma, Bao-Dong Cui, Wen-Yong Han, Yong-Zheng Chen
Summary: An efficient enzymatic process has been developed for the synthesis of valuable compounds through catalytic kinetic resolution, demonstrating synthetic utility and scalability.
Review
Chemistry, Multidisciplinary
Shuke Wu, Radka Snajdrova, Jeffrey C. Moore, Kai Baldenius, Uwe T. Bornscheuer
Summary: Biocatalysis is widely used as an alternative to chemical catalysis in various fields, with enzymes playing a key role in organic synthesis, particularly in the production of chiral compounds for pharmaceuticals and flavors. Biocatalysts are also utilized on a large scale for the production of specialty and bulk chemicals. This review focuses on scalable chemical production using enzymes, discussing opportunities, limitations, and emerging enzyme classes through illustrative examples.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Physical
Lia Martinez-Montero, Dirk Tischler, Philipp Suess, Anett Schallmey, Maurice C. R. Franssen, Frank Hollmann, Caroline E. Paul
Summary: A biocatalytic cascade was developed for the synthesis of enantioenriched azido alcohols, introducing chiral substituents through enzymatic epoxidation and regioselective cleavage reactions, leading to highly enantioenriched aromatic azido alcohols. This approach demonstrates the potential for practical production of these chiral compounds using two-component flavoprotein monooxygenases.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Multidisciplinary
Luca Deiana, Abdolrahim A. Rafi, Veluru Ramesh Naidu, Cheuk-Wai Tai, Jan-E Backvall, Armando Cordova
Summary: The assembly of cellulose-based artificial plant cell wall structures with different types of catalysts is a powerful strategy for developing cascade reactions, such as transforming a racemic amine into enantiomerically pure amide in high yield by a dynamic kinetic resolution catalytic system containing a lipase enzyme and nanopalladium particles.
CHEMICAL COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Lin-Xin Ruan, Bo Sun, Jia-Ming Liu, Shi-Liang Shi
Summary: Despite the importance of enantioenriched tertiary alcohols bearing two contiguous stereocenters, their efficient synthesis has remained a challenge. In this study, we report a platform for their preparation using nickel-catalyzed addition of organoboronates to racemic ketones, achieving high levels of diastereo- and enantioselectivity.
Article
Biochemistry & Molecular Biology
Jan Samsonowicz-Gorski, Anna Brodzka, Ryszard Ostaszewski, Dominik Koszelewski
Summary: This paper describes a new strategy for the simultaneous double chemoselective kinetic resolution of chiral amines and alcohols, using carbonate as the catalyst and chiral organic carbonates as the acyl donors. The method exhibits high enantioselectivity and chemoselectivity, and has the potential for synthesizing enantiopure organic precursors of valuable compounds.
Article
Chemistry, Multidisciplinary
Stefano Fogal, Elisabetta Bergantino, Riccardo Motterle
Summary: This work presents the enantioselective resolution of a water-soluble racemic mixture catalyzed by Candida antarctica lipase B, achieving both separation and efficient utilization of the products.
Article
Chemistry, Physical
Jacob S. DeHovitz, Todd K. Hyster
Summary: Isomerizations are chemical processes that transform a compound into a different structure while maintaining the same chemical formula. The recent resurgence of photochemistry has led to an increased focus on using radicals and diradicals as key intermediates for isomerization. Understanding the mechanisms behind these approaches can help streamline chemical synthesis.
