Article
Chemistry, Multidisciplinary
Vasilis Tseliou, Adriana Faraone, Laura Kqiku, Jan Vilim, Gianluca Simionato, Paolo Melchiorre
Summary: This study introduces a novel strategy for biocascades using a single multifunctional enzyme to promote multiple stereoselective steps in a domino process by mastering distinct catalytic mechanisms, simplifying the synthesis of chiral molecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Applied
Xing Wang, Xuling Chen, Wei Lin, Pengfei Li, Wenjun Li
Summary: Axially chiral allenes are important natural products and synthetic molecules with significant biological activity. The catalytic enantioselective synthesis of these compounds has been widely studied, and many simple and efficient methods have been developed, thanks to the advancements in asymmetric organocatalysis.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Article
Chemistry, Multidisciplinary
Qing-Qing Hang, Shu-Fang Wu, Shuang Yang, Xue Wang, Zhen Zhong, Yu-Chen Zhang, Feng Shi
Summary: The catalytic atroposelective synthesis of axially chiral isochromenone-indoles has been achieved using homophthalic anhydride-based indole derivatives as a new platform molecule for dynamic kinetic resolution. A wide range of axially chiral isochromenone-indoles were synthesized in high yields and excellent enantioselectivities using chiral quaternary ammonium salt as a phase-transfer catalyst in the catalytic asymmetric sulfonylation reaction.
SCIENCE CHINA-CHEMISTRY
(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
Ke-Wei Chen, Zhi-Han Chen, Shuang Yang, Shu-Fang Wu, Yu-Chen Zhang, Feng Shi
Summary: A new strategy has been developed for the highly atroposelective synthesis of N-N axially chiral indole scaffolds and bispyrroles, which can be used as chiral organocatalysts and exhibit potent anticancer activity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Christian Ascaso-Alegre, Raquel P. Herrera, Juan Mangas-Sanchez
Summary: The combination of small-molecule catalysis and enzyme catalysis shows great potential in asymmetric synthetic chemistry. The one-pot three-step chemoenzymatic cascade combination described in this study allows for efficient synthesis of chiral nitro alcohols with high overall yields and excellent selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Qi Zhang, Yao Li, Long Zhang, Sanzhong Luo
Summary: A novel three-component Lewis acid-base catalyst has been developed, utilizing a bulky tertiary amine to activate a Lewis pair for enamine catalysis, allowing for asymmetric control of disulfuration reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
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
Biochemistry & Molecular Biology
Christian M. Heckmann, Lucia Robustini, Francesca Paradisi
Summary: This study investigates the importance of enzymatic enantiopreference in biocatalysis, revealing that increasing substrate loadings can lead to the inversion of enantiopreference, and adjusting the ionic strength or co-solvent content in the reaction mixture can alter enantiopreference.
Article
Chemistry, Multidisciplinary
Si-Jia Liu, Zhi-Han Chen, Jia-Yi Chen, Shao-Fei Ni, Yu-Chen Zhang, Feng Shi
Summary: A new class of axially chiral styrene-based thiourea tertiary amine catalysts with efficient synthetic route, multiple chiral elements, and multiple activating groups has been designed. These catalysts have proven to be efficient in enabling the cyclization reaction of 2-benzothiazolimines and homophthalic anhydrides with high yields and excellent stereoselectivities. The role of axially chiral styrene moiety in controlling reactivity and enantioselectivity has been elucidated through theoretical calculations.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Feng-Tao Sheng, Shuang Yang, Shu-Fang Wu, Yu-Chen Zhang, Feng Shi
Summary: A new strategy for the enantioselective synthesis of axially chiral 3,3'-bisindoles was developed by directly coupling two indole rings using the C3-umpolung reactivity of 2-indolylmethanols. The synthesized compounds can be further modified to create axially chiral 3,3'-bisindole-based organocatalysts for asymmetric catalysis.
CHINESE JOURNAL OF CHEMISTRY
(2022)
Article
Chemistry, Organic
Miglena K. Georgieva, A. Gil Santos
Summary: The Diels-Alder reaction is a fascinating chemical process that has been extensively studied, both in its achiral and chiral versions. In this study, the authors investigate the Diels-Alder reaction of 2'-hydroxychalcones with two dienes, catalyzed by chiral organo-boron Lewis acid complexes. The authors use theoretical methods to evaluate the proposed reaction mechanism and provide insights into the enantioselectivity and endo/exo selectivity of the reaction.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Applied
I-Ting Chen, Ren-You Guan, Jeng-Liang Han
Summary: In this study, a catalytic asymmetric vinylogous Mannich/annulation/acylation reaction was developed for the synthesis of chiral spiro-oxindole piperidine derivatives with polyaromatic scaffolds. The reaction provided the desired products in good yields and high enantioselectivity. DFT computational calculations were used to explain the mechanism and origin of the observed enantioselectivity and O-acetylated products.
ADVANCED SYNTHESIS & CATALYSIS
(2022)
Review
Chemistry, Organic
Tingting Li, Qian Zhou, Fanjing Meng, Wenhui Cui, Qian Li, Jiang Zhu, Yang Cao
Summary: This review provides a summary of the recent advances in organocatalytic and biocatalytic asymmetric reductive amination (ARA), which is a challenging but significant topic for drug discovery and the pharmaceutical industry. ARA can be categorized into three types: metal catalysis, organic catalysis, and biocatalysis. Transition metal-catalyzed ARA has been well-established, while organocatalytic ARA has emerged as a powerful alternative. Biocatalytic ARA has also shown remarkable progress in the past decade, with the successful utilization of various enzymes.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2023)
Review
Chemistry, Organic
Christian Ascaso-Alegre, Juan Mangas-Sanchez
Summary: Inspired by nature, synthetic chemists are trying to mimic the efficient metabolic networks in living organisms to build complex molecules by combining different types of catalysts in the same reaction vessel. This highly multidisciplinary field benefits from advances in chemical catalysis, molecular biology and reaction engineering, and is rapidly progressing towards higher productivity and lower waste generation and cost in synthetic procedures.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Biochemistry & Molecular Biology
Fabricio R. Bisogno, Rosario Fernandez, Jose Maria Lassaletta, Gonzalo de Gonzalo
Summary: Room temperature ionic liquids (RTILs) have shown positive effects in organic catalysis, enhancing catalyst activity, lowering reaction temperatures, and improving yields and enantioselectivity.
Article
Biochemistry & Molecular Biology
Gonzalo de Gonzalo
Summary: Cyrene™ is a new polar solvent that has shown beneficial effects on bioreduction conversions in enzyme-catalyzed reactions. Its presence at a certain concentration can improve reaction rates and optical purities of the products.
BIOCATALYSIS AND BIOTRANSFORMATION
(2022)
Review
Biotechnology & Applied Microbiology
Carmen Aranda, Juan Carro, Alejandro Gonzalez-Benjumea, Esteban D. Babot, Andres Olmedo, Dolores Linde, Angel T. Martinez, Ana Gutierrez
Summary: Selective oxyfunctionalizations of aliphatic compounds are challenging chemical reactions, but enzymes such as P450 monooxygenases and unspecific peroxygenases (UPOs) play important roles due to their stereo- and regio-selectivity. UPOs, discovered in fungi, have emerged as promising biocatalysts for their ability to catalyze the oxyfunctionalization of aliphatic and aromatic compounds using only H2O2.
BIOTECHNOLOGY ADVANCES
(2021)
Review
Chemistry, Physical
Gonzalo de Gonzalo, Andres R. Alcantara
Summary: Baeyer-Villiger monooxygenases (BVMOs) are flavin-dependent oxidative enzymes that catalyze the transformation of linear and cyclic ketones into esters and lactones by inserting an oxygen atom between a carbonylic Csp(2) and the Csp(3) at the alpha position. BVMOs can be included in cascade reactions with other redox enzymes, such as alcohol dehydrogenases or ene-reductases, to achieve the direct conversion of alcohols or alpha,beta-unsaturated carbonylic compounds into the corresponding esters. Employing multienzymatic strategies with BVMOs using whole cells or isolated enzymes in sequential or parallel methods can highlight the advantages and recent advances for overcoming drawbacks when using BVMOs in these techniques.
Editorial Material
Biochemistry & Molecular Biology
Gonzalo de Gonzalo, Mara G. Freire
Article
Biochemistry & Molecular Biology
Gonzalo de Gonzalo, Nikola Loncar, Marco Fraaije
Summary: 5-Hydroxymethylfurfural oxidase (HMFO) is a useful biocatalyst for selective oxidation of alcohols using oxygen as a mild oxidant without expensive organic cofactors. Both wild-type HMFO and an engineered thermostable variant have shown good catalytic performance in the kinetic resolution of various benzofused alcohols. The use of natural deep eutectic solvents (NADES) has also been explored for HMFO-catalyzed alcohol oxidation, showing improved conversion and selectivity for racemic 1-indanol with different NADES, especially those containing carbohydrates. Proper selection of biocatalyst and NADES can provide good enantioselectivity, demonstrating the advantages of using these solvents in biocatalytic processes.
BIOCATALYSIS AND BIOTRANSFORMATION
(2023)
Article
Chemistry, Multidisciplinary
Gonzalo de Gonzalo, Caroline E. Paul
Summary: This review discusses recent advances in the application of alcohol dehydrogenases in cascade reactions, collaborating with other enzyme classes, chemocatalysts, or organocatalysts to obtain high value-added products such as chiral diols and amino alcohols. The review also looks towards future developments in chemoenzymatic and organoenzymatic cascades.
CURRENT OPINION IN GREEN AND SUSTAINABLE CHEMISTRY
(2021)
Review
Chemistry, Medicinal
Gonzalo de Gonzalo, Andres R. Alcantara
Summary: The beta-dicarbonyl structure is a key component in many biologically and pharmaceutically active compounds, with potential therapeutic effects on various pathological disorders, making it a popular topic of interest among organic chemists. Various methods have been developed for the preparation of 1,3-diketones, as well as for the synthesis of branched beta-dicarbonyl compounds through alpha-functionalization of non-substituted 1,3-diketones.
Article
Biochemistry & Molecular Biology
Dolores Linde, Alejandro Gonzalez-Benjumea, Carmen Aranda, Juan Carro, Ana Gutierrez, Angel T. Martinez
Summary: Vegetable oils are valuable renewable resources for the production of bio-based chemicals and intermediates. Enzymes can be used as environmentally friendly alternatives to chemical catalysis in the epoxidation reactions of vegetable oils. By engineering the active site of the enzyme and optimizing the process, the epoxidation yield can be significantly enhanced.
Article
Biochemistry & Molecular Biology
Esteban D. Babot, Carmen Aranda, Jan Kiebist, Katrin Scheibner, Rene Ullrich, Martin Hofrichter, Angel T. Martinez, Ana Gutierrez
Summary: Terminal alkenes are attractive starting materials for synthesizing epoxides, which are crucial intermediate building blocks in various industries. Researchers have explored the use of unspecific peroxygenases (UPOs) as biocatalysts for selectively epoxidizing terminal alkenes. Several UPOs have demonstrated the ability to catalyze the epoxidation of long-chain terminal alkenes with different selectivities and turnover rates. This approach offers a green and potential alternative to existing synthesis technologies.
Article
Biochemistry & Molecular Biology
Gonzalo de Gonzalo, Nikola Loncar, Marco Fraaije
Summary: The Baeyer-Villiger monooxygenase OTEMO from Pseudomonas putida ATCC 17453 has been utilized as a biocatalyst for the asymmetric synthesis of optically active sulphoxides. Good to high enantiopurities can be achieved for substrates with electron-donating groups, but low enantioselectivities are observed during kinetic resolution of racemic sulphoxides. Various factors including pH, temperature, organic cosolvents, and substrate concentration have been investigated to determine the biocatalytic potential of OTEMO.
BIOCATALYSIS AND BIOTRANSFORMATION
(2022)
Review
Biochemistry & Molecular Biology
Margherita Miele, Veronica Pillari, Vittorio Pace, Andres R. Alcantara, Gonzalo de Gonzalo
Summary: The development of green solvents with renewable properties has provided an environmentally friendly alternative for synthesizing optically active compounds.
Article
Chemistry, Multidisciplinary
Patricia Gomez de Santos, Alejandro Gonzalez-Benjumea, Angela Fernandez-Garcia, Carmen Aranda, Yinqi Wu, Andrada But, Patricia Molina-Espeja, Diana M. Mate, David Gonzalez-Perez, Wuyuan Zhang, Jan Kiebist, Katrin Scheibner, Martin Hofrichter, Katarzyna Swiderek, Vicent Moliner, Julia Sanz-Aparicio, Frank Hollmann, Ana Gutierrez, Miguel Alcalde
Summary: In this study, a highly regioselective fungal peroxygenase was engineered for the omega-1 hydroxylation of fatty acids. The selective biocatalyst was produced by Pichia pastoris and successfully used for the preparative synthesis of (omega-1)-hydroxytetradecanoic acid with high regioselectivity and enantiomeric excess.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(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.
Review
Chemistry, Physical
Pedro D. Garcia-Fernandez, Juan M. Coto-Cid, Gonzalo de Gonzalo
Summary: Asymmetric oxidation processes are a valuable tool for synthesizing active pharmaceutical ingredients (APIs), especially optically active sulfoxides with interesting biological properties. Traditional approaches often use hazardous reagents and solvents, which are unsustainable. In recent decades, chemists have been combining the preparation of valuable compounds with sustainable protocols using greener solvents, reagents, and catalysts, as well as novel techniques like flow catalysis or photocatalysis. This review focuses on the latest efforts in developing greener approaches, with a focus on biocatalytic methods and the use of mild reaction conditions and reagents, as well as other novel techniques such as photocatalysis.