Recent Advance in Organocatalyzed Asymmetric Reduction of Prochiral Ketones: An Update

Synthesis ◽  
2021 ◽  
Author(s):  
Xu-Long Qin ◽  
Li-Jun Xu ◽  
Fu-She Han
Keyword(s):  
Asymmetric Reduction ◽  
Building Blocks ◽  
Short Review ◽  
Chiral Alcohols ◽  
Comprehensive Overview ◽  
Synthetic Intermediates ◽  
Prochiral Ketones ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Easy Operation

Chiral alcohols are important synthetic intermediates or building blocks for the diverse synthesis of drugs, agrochemicals, and natural products. Asymmetric reduction of prochiral ketones has been the most popularly investigated method for accessing chiral alcohols. In this regard, the organocatalyzed asymmetric reduction as a complementary of transition-metal- and enzyme-catalyzed reactions have attracted tremendous interest in the past decades due to the nature of metal-free and easy operation, as well as, principly, the ease of recovery and reuse of catalysts. Following up a comprehensive overview on organocatalyzed asymmetric reduction of prochiral ketones in early 2018, this short review is intended to summarize the recent progress in this area from the beginning of the year 2018 to the end of Aug. 2021.

Enantioselective Catalytic Methods for the Elaboration of Chiral Tetrahydro-β-carbolines and Related Scaffolds

Synthesis ◽  
2017 ◽  
Vol 49 (12) ◽  
pp. 2605-2620 ◽  
Author(s):  
Nicolas Glinsky-Olivier ◽  
Xavier Guinchard
Keyword(s):  
Kinetic Resolution ◽  
Asymmetric Reduction ◽  
Asymmetric Hydrogenation ◽  
Transfer Hydrogenation ◽  
Chiral Molecules ◽  
Chiral Phosphoric Acid ◽  
Hydrogenation Reactions ◽  
Synthetic Intermediates ◽  
Catalyzed Reactions

Tetrahydro-β-carbolines are important synthetic intermediates in the total synthesis of natural products and of compounds exhibiting strong bioactivities. Over the last decades, catalytic methods using chiral catalysts have been described for their synthesis. This review covers catalytic and enantioselective methods to access chiral tetrahydro-β-carbolines and their applications in the elaboration of complex chiral molecules.1 Introduction2 Asymmetric Reduction of Dihydro-β-carbolines2.1 Asymmetric Transfer Hydrogenation Reactions2.2 Asymmetric Hydrogenation Reactions2.3 Biocatalyzed Reduction of Dihydro-β-carbolines3 Organocatalyzed Pictet–Spengler Reactions3.1 Chiral Thiourea-Catalyzed Reactions3.2 Chiral Phosphoric Acid Catalyzed Reactions4 Pictet–Spengler Reactions of In Situ Generated Cyclic Iminiums5 Organocatalyzed Functionalization of Dihydro-β-carboliniums6 Organocatalyzed Alkylation of Tetrahydro-β-carbolines7 Biocatalyzed Dynamic Kinetic Resolution of Tetrahydro-β-carbolines8 Conclusion and Perspectives

Production of chiral alcohols from prochiral ketones by microalgal photo-biocatalytic asymmetric reduction reaction

2012 ◽  
Vol 39 (6) ◽  
pp. 835-841 ◽  
Author(s):  
Zhong-Hua Yang ◽  
Li Luo ◽  
Xu Chang ◽  
Wei Zhou ◽  
Geng-Hua Chen ◽  
...  
Keyword(s):  
Asymmetric Reduction ◽  
Reduction Reaction ◽  
Chiral Alcohols ◽  
Prochiral Ketones

Asymmetric Reduction of Prochiral Ketones to Chiral Alcohol by Photo-Biocatalysis with Microalgae

2013 ◽  
Vol 803 ◽  
pp. 60-63
Author(s):  
Geng Hua Chen ◽  
Sen Xiang Zhang ◽  
Qiao Hu ◽  
Xin Xing Deng ◽  
Fang Yu ◽  
...  
Keyword(s):  
Ethyl Acetoacetate ◽  
Spirulina Platensis ◽  
Asymmetric Reduction ◽  
Scenedesmus Obliquus ◽  
Reduction Reaction ◽  
Chiral Alcohols ◽  
Chiral Alcohol ◽  
Prochiral Ketones

The photo-biocatalytic ability of eukaryotic microalgae and prokaryotic microalgae on nonnatural prochiral ketones to produce chiral alcohols was studied in this paper. The results proved that ethyl acetoacetate and acetophenone can be stereo-selectively reduced to the corresponding ethyl S-3-hydroxybutyrate (EHB) and S-1-phenylethanol (PEA) by microalgal photo-biocatalysis with high enantioselectivity, respectively. Scenedesmus obliquus has the best photo-biocatalytic activity to ethyl acetoacetate reduction reaction among the two selected eukaryotic microalgae, about 43.98% yield and 69.58% e.e. achieved. Spirulina platensis is the best biocatalyst to acetophenone among the four selected prokaryotic microalgae, about 52.65% yield and 99.40% e.e. achieved.

Asymmetric reduction of prochiral ketones to chiral alcohols catalyzed by plants tissue

2008 ◽  
Vol 35 (9) ◽  
pp. 1047-1051 ◽  
Author(s):  
Zhong-Hua Yang ◽  
Rong Zeng ◽  
Gai Yang ◽  
Yu Wang ◽  
Li-Zhen Li ◽  
...  
Keyword(s):  
Asymmetric Reduction ◽  
Chiral Alcohols ◽  
Prochiral Ketones

scholarly journals Formation Mechanism and Biomedical Applications of Protease-Manipulated Peptide Assemblies

2021 ◽  
Vol 9 ◽  
Author(s):  
Tianyue Jiang ◽  
Chendan Liu ◽  
Xiao Xu ◽  
Bingfang He ◽  
Ran Mo
Keyword(s):  
Biomedical Applications ◽  
Enzymatic Catalysis ◽  
Building Blocks ◽  
Molecular Assembly ◽  
Bond Forming ◽  
Peptide Assembly ◽  
Non Covalent Interactions ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Matrix Construction

Exploiting enzyme-catalyzed reactions to manipulate molecular assembly has been considered as an attractive bottom-up nanofabrication approach to developing a variety of nano-, micro-, and macroscale structures. Upon enzymatic catalysis, peptides and their derivatives transform to assemblable building blocks that form ordered architecture by non-covalent interactions. The peptide assemblies with unique characteristics have great potential for applications in bionanotechnology and biomedicine. In this mini review, we describe typical mechanisms of the protease-instructed peptide assembly via bond-cleaving or bond-forming reactions, and outline biomedical applications of the peptide assemblies, such as drug depot, sustained release, controlled release, gelation-regulated cytotoxicity, and matrix construction.

scholarly journals One-step catalytic asymmetric synthesis of all-syn deoxypropionate motif from propylene: Total synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid

2016 ◽  
Vol 113 (11) ◽  
pp. 2857-2861 ◽  
Author(s):  
Yusuke Ota ◽  
Toshiki Murayama ◽  
Kyoko Nozaki
Keyword(s):  
Building Blocks ◽  
Single Step ◽  
Enzymatic Reactions ◽  
Stereogenic Centers ◽  
Complex Building ◽  
One Step ◽  
Simple Molecules ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Major Acid

In nature, many complex structures are assembled from simple molecules by a series of tailored enzyme-catalyzed reactions. One representative example is the deoxypropionate motif, an alternately methylated alkyl chain containing multiple stereogenic centers, which is biosynthesized by a series of enzymatic reactions from simple building blocks. In organic synthesis, however, the majority of the reported routes require the syntheses of complex building blocks. Furthermore, multistep reactions with individual purifications are required at each elongation. Here we show the construction of the deoxypropionate structure from propylene in a single step to achieve a three-step synthesis of (2R,4R,6R,8R)-2,4,6,8-tetramethyldecanoic acid, a major acid component of a preen-gland wax of the graylag goose. To realize this strategy, we focused on the coordinative chain transfer polymerization and optimized the reaction condition to afford a stereo-controlled oligomer, which is contrastive to the other synthetic strategies developed to date that require 3–6 steps per unit, with unavoidable byproduct generation. Furthermore, multiple oligomers with different number of deoxypropionate units were isolated from one batch, showing application to the construction of library. Our strategy opens the door for facile synthetic routes toward other natural products that share the deoxypropionate motif.

Reactions of Arynes Involving Transition-Metal Catalysis

Synthesis ◽  
2017 ◽  
Vol 28 (19) ◽  
pp. 4414-4433 ◽  
Author(s):  
Xuefeng Jiang ◽  
Minghao Feng
Keyword(s):  
Transition Metal ◽  
Multicomponent Reactions ◽  
Building Blocks ◽  
Short Review ◽  
Aromatic Rings ◽  
Metal Catalysis ◽  
Cascade Cyclizations ◽  
Catalyzed Reactions ◽  
Metal Catalyzed ◽  
Harsh Conditions

Arynes are important building blocks for introducing aromatic rings into molecules and they are frequently utilized in syntheses. Historically, arynes were generated under harsh conditions and this limited their use. Arynes can now be generated under milder conditions, e.g. from 2-(trimethylsilyl)phenyl triflate, and utilized in transition-metal­ catalyzed reactions such as [2+2+2] reactions, insertion into σ-bonds, cascade cyclizations and C–H activation reactions. This short review focuses on transition-metal-catalyzed reactions relevant to aryne intermediates generated from 2-(trimethylsilyl)phenyl triflates and other aryne precursors.1 Introduction2 [2+2+2] Reactions3 Aryne Insertion into a σ-Bond4 Cascade Cyclizations5 C–H Activation6 Multicomponent Reactions (MCRs)7 Conclusion

Design of an in vitro biocatalytic cascade for the manufacture of islatravir

Science ◽  
2019 ◽  
Vol 366 (6470) ◽  
pp. 1255-1259 ◽  
Author(s):  
Mark A. Huffman ◽  
Anna Fryszkowska ◽  
Oscar Alvizo ◽  
Margie Borra-Garske ◽  
Kevin R. Campos ◽  
...  
Keyword(s):  
Chemical Synthesis ◽  
Directed Evolution ◽  
Building Blocks ◽  
Hiv Treatment ◽  
Pharmaceutical Manufacturing ◽  
Enzymatic Reactions ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions

Enzyme-catalyzed reactions have begun to transform pharmaceutical manufacturing, offering levels of selectivity and tunability that can dramatically improve chemical synthesis. Combining enzymatic reactions into multistep biocatalytic cascades brings additional benefits. Cascades avoid the waste generated by purification of intermediates. They also allow reactions to be linked together to overcome an unfavorable equilibrium or avoid the accumulation of unstable or inhibitory intermediates. We report an in vitro biocatalytic cascade synthesis of the investigational HIV treatment islatravir. Five enzymes were engineered through directed evolution to act on non-natural substrates. These were combined with four auxiliary enzymes to construct islatravir from simple building blocks in a three-step biocatalytic cascade. The overall synthesis requires fewer than half the number of steps of the previously reported routes.

A kinetic analysis of coupled sequential enzyme reactions

2018 ◽  
Author(s):  
Justin Eilertsen ◽  
Santiago Schnell
Keyword(s):  
Enzyme Assay ◽  
Sequential Reaction ◽  
Enzyme Reactions ◽  
Indicator Reaction ◽  
Single Substrate ◽  
Complex Sequences ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Single Enzyme

<div>As a case study, we consider a coupled enzyme assay of sequential enzyme reactions obeying the Michaelis--Menten reaction mechanism. The sequential reaction consists of a single-substrate, single-enzyme non-observable reaction followed by another single-substrate, single-enzyme observable reaction (indicator reaction). In this assay, the product of the non-observable reaction becomes the substrate of the indicator reaction. A mathematical analysis of the reaction kinetics is performed, and it is found that after an initial fast transient, the sequential reaction is described by a pair of interacting Michaelis--Menten equations. Timescales that approximate the respective lengths of the indicator and non-observable reactions, as well as conditions for the validity of the Michaelis--Menten equations are derived. The theory can be extended to deal with more complex sequences of enzyme catalyzed reactions.</div>

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