Article
Chemistry, Organic
Zaneta Papadopulu, Martin Oestreich
Summary: A method for the nonenzymatic kinetic resolution of sterically congested alcohols with a quaternary carbon atom in the beta-position is reported, using the catalyst system CuCl/NaOtBu/(R,R)-Ph-BPE together with a 3,5-xylyl-substituted tertiary hydrosilane to achieve enantioselective silylation of the hydroxy group. Several alcohols are obtained with good to excellent selectivity factors, and there are currently no other known straightforward methods to access these motifs.
Article
Chemistry, Organic
Jian Song, Wen-Hua Zheng
Summary: A highly enantioselective method for the kinetic resolution of racemic tertiary alcohols has been developed using chiral organotin-catalyzed intermolecular acylation. The process can be carried out under mild reaction conditions and has a broad substrate scope, allowing for the separation of the corresponding products and highly enantioselective recovery of tertiary alcohols with s factors up to >200.
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
Chemistry, Physical
Masa Sterle, Matej Hus, Matic Lozinsek, Anamarija Zega, Andrej Emanuel Cotman
Summary: Stereopure CF3-substituted syn-1,2-diols were synthesized through the reductive dynamic kinetic resolution of corresponding alkyl ketones, yielding products with >95% ee and >87:13 syn/anti ratio. This method provides a rapid access to stereopure bioactive molecules. Moreover, DFT calculations were conducted on three types of Noyori-Ikariya ruthenium catalysts to demonstrate their general ability to control stereoselectivity through hydrogen bond acceptor SO2 region and CH/pi interactions.
Article
Chemistry, Multidisciplinary
Xintuo Yang, Xiang Li, Pinhong Chen, Guosheng Liu
Summary: A novel Pd(II)-catalyzed enantioselective Markovnikov hydrooxygenation of unactivated terminal alkenes using a substituted pyridinyl oxazoline (Pyox) ligand has been developed. The (EtO)(2)MeSiH/BQ redox system is crucial for the highly selective and efficient hydrooxygenation, where alkylpalladium(II) species generated from enantioselective oxypalladation step is reduced by silane. This method provides an efficient access to optically pure alcohol esters from easily available alkenes with excellent enantioselectivities and features a broad substrate scope.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Physical
Martin Soto, Vicente Gotor-Fernandez, Humberto Rodriguez-Solla, Walter Baratta
Summary: The transfer hydrogenation of flavanones and ortho-hydroxychalcones catalyzed by ruthenium pincer complexes allows the synthesis of ortho-hydroxy 1,3-diarypropanols with high yield and selectivity. The amount of co-catalyst is crucial for the reduction reaction, while using pincer catalysts with specific ligands can achieve high enantiomeric excess and moderate conversion rates in the reduction of flavanones.
Article
Chemistry, Organic
Titouan Desrues, Xueyang Liu, Jean-Marc Pons, Valerie Monnier, Jean-Arthur Amalian, Laurence Charles, Adrien Quintard, Cyril Bressy
Summary: This study introduces a new method for the enantioselective synthesis of tertiary alcohols through a chiral isothiourea catalyzed selective acylation of adjacent secondary alcohols, allowing for the preparation of highly enantioenriched monoesters and starting diols. The approach enables the kinetic resolution of racemic diastereoenriched secondary/tertiary diols with s-values exceeding 200.
Article
Chemistry, Multidisciplinary
Juan Liu, Yi-Ying Du, Yu-Shi He, Yan Liang, Shang-Zhong Liu, Yi-Yi Li, Yi-Ming Cao
Summary: In this study, a chiral phosphoric acid catalyzed apparent hydrolytic ring-opening reaction was developed for racemic aziridines in a regiodivergent parallel kinetic resolution manner. Through the acyloxy-assisted strategy, highly stereocontrolled nucleophilic ring-opening of aziridines with water was achieved, resulting in enantioenriched amino alcohols with high yields and enantiomeric ratios.
Review
Chemistry, Organic
Ricardo Molina Betancourt, Pierre-Georges Echeverria, Tahar Ayad, Phannarath Phansavath, Virginie Ratovelomanana-Vidal
Summary: This short review focuses on the development of efficient, atom-economical, and sustainable methods for the production of chiral alcohols and amines, particularly through homogeneous asymmetric catalysis. It discusses asymmetric hydrogenation and transfer hydrogenation, as well as dynamic kinetic resolution as key approaches to constructing up to three stereogenic centers.
SYNTHESIS-STUTTGART
(2021)
Review
Chemistry, Organic
Tianyu Peng, Shixin Li, Dongxu Yang, Linqing Wang
Summary: Kinetic resolution is a practical method that selectively recovers enantiomerically pure starting materials and products from racemic mixtures. In this review, the less explored intramolecular kinetic resolution is discussed, highlighting its importance and elegance in generating chiral scaffolds. Different reaction types, including cyclization, elimination, isomerization, rearrangement, and miscellaneous reactions, are systematically presented and analyzed.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Kun Wang, Saisai Niu, Xin Guo, Weijun Tang, Dong Xue, Jianliang Xiao, Huaming Sun, Chao Wang
Summary: This research discovers a new method to convert prochiral racemic allylic alcohols to enantioenriched chiral alcohols bearing adjacent stereocenters using a diamine diphosphine Ru complex and tBuOK catalyst. The protocol exhibits a wide substrate scope and high selectivities, and can be applied to the synthesis of enantioenriched chromane and indane compounds.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
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
Ting Chen, Wenjun Liu, Wei Gu, Shengtong Niu, Shouang Lan, Zhifei Zhao, Fan Gong, Jinggong Liu, Shuang Yang, Andrej Emanuel Cotman, Jinshuai Song, Xinqiang Fang
Summary: In this study, a unique dynamic kinetic resolution (DKR) mode was used to achieve the highly selective semi-transfer hydrogenation of unsymmetrical alpha-diketones. The distal carbonyl group was reduced while the proximal carbonyl remained untouched, resulting in the synthesis of enantioenriched acyclic ketones with alpha-hydroxy-alpha'-C(sp2)-functional groups. These products represent a new class of compounds that have not been previously reported. The utility of the synthesized compounds was demonstrated through further transformations, including the rapid synthesis of drug molecules. DFT calculations and control experiments were conducted to gain mechanistic insights into the highly selective semihydrogenation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Physical
Jose A. Carmona, Carlos Rodriguez-Franco, Joaquin Lopez-Serrano, Abel Ros, Javier Iglesias-Siguenza, Rosario Fernandez, Jose M. Lassaletta, Valentin Hornillos
Summary: An efficient dynamic kinetic resolution (DKR) approach has been developed for the synthesis of axially chiral diamines based on ruthenium-catalyzed enantioselective transfer hydrogenation. This method features a broad substrate scope and proceeds under very mild conditions, allowing the preparation of BINAM homologues in good to high yields and nearly perfect enantioselectivities (up to 99% ee).
Article
Multidisciplinary Sciences
Ahreum Kim, Chanhee Lee, Jayoung Song, Sang Kook Lee, Yongseok Kwon
Summary: In this study, a flexible platform for chiral phosphoric acid-catalyzed atroposelective dynamic kinetic resolution was reported using o-amidobiaryl as the substrate. The platform demonstrated excellent enantioselectivity control over substrates with different aromatic ring positions when reacted with ketomalonate in the presence of chiral phosphoric acid. Computational investigation highlighted the importance of the NH group in determining the enantioselectivity. Furthermore, the scaffold showed good efficacy in antiproliferative effects.
NATURE COMMUNICATIONS
(2023)
Review
Biochemistry & Molecular Biology
Wen-Ju Bai, Xiqing Wang
NATURAL PRODUCT REPORTS
(2017)
Article
Chemistry, Multidisciplinary
Barry M. Trost, Wen-Ju Bai, Christoph Hohn, Yu Bai, James J. Cregg
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Organic
Wen-Ju Bai, Thomas R. R. Pettus
Article
Chemistry, Physical
Chen Lu, Fenglin Shen, Shuaibo Wang, Yuyang Wang, Juan Liu, Wen-Ju Bai, Xiqing Wang
Article
Chemistry, Multidisciplinary
Barry M. Trost, Wen-Ju Bai, Craig E. Stivala, Christoph Hohn, Caroline Poock, Marc Heinrich, Shiyan Xu, Jullien Rey
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2018)
Article
Chemistry, Organic
Xiu Gu, Hao Yuan, Jun Jiang, Yi Wu, Wen-Ju Bai
Article
Chemistry, Organic
Barry M. Trost, Christopher A. Kalnmals, Jacob S. Tracy, Wen-Ju Bai
Article
Chemistry, Multidisciplinary
Barry M. Trost, Yu Bai, Wen-Ju Bai, Johnathan E. Schultz
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2019)
Article
Chemistry, Organic
Yang Liu, Peng Xie, Jiagen Li, Wen-Ju Bai, Jun Jiang
Article
Chemistry, Multidisciplinary
Jiayang Zhang, Yangtian Yan, Rong Hu, Ting Li, Wen-Ju Bai, Yang Yang
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Yanxin Wei, Chen Lu, Shengsheng Jiang, Yanyan Zhang, Qiuchun Li, Wen-Ju Bai, Xiqing Wang
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Barry M. Trost, James J. Cregg, Christoph Hohn, Wen-Ju Bai, Guoting Zhang, Jacob S. Tracy
Article
Chemistry, Physical
Shuaibo Wang, Shengsheng Jiang, Hao Chen, Wen-Ju Bai, Xiqing Wang
Article
Chemistry, Physical
Hao Chen, Mengfei Huang, Wenliang Yan, Wen-Ju Bai, Xiqing Wang
Summary: Directed evolution of a P450 hydroxylase leads to a highly selective engineered enzyme capable of catalyzing the oxyfunctionalization of fatty acids. This biocatalyst displays high reactivity and can convert a variety of fatty acids to optically pure beta-hydroxy fatty acids, offering a chemoenzymatic strategy to access valuable fatty acid derivatives. Molecular docking studies provide insight into the regio- and enantioselectivity of this reaction.
Article
Chemistry, Multidisciplinary
Kun Zhang, Aiqin Yu, Xuan Chu, Fudong Li, Juan Liu, Lin Liu, Wen-Ju Bai, Chao He, Xiqing Wang
Summary: Selective hydroxylation of non-activated aliphatic C-H bonds was achieved through directed evolution of P450(BS beta) hydroxylase. The reaction showed high selectivity towards various aliphatic carboxylic acids with different chain lengths, functional groups, and aromatic moieties. The X-ray structure of the evolved enzyme variant provided insights into the regio- and enantioselectivity of the reaction.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
