Controlled One‐Pot Synthesis of Multiple Heterocyclic Scaffolds Based on an Amphiphilic Claisen‐Schmidt Reaction Intermediate

Song, Rong; Yu, Hui Qun; Huang, Haowen; Chen, Yun

doi:10.1002/slct.201904110

Cited by 8 publications

(10 citation statements)

References 70 publications

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“…When using 2carboxybenzaldehyde, the resulting product was the lactone (1c) rather than the corresponding α,β-unsaturated 2-keto acid due to intramolecular conjugate addition during acidic workup, which is well documented in the literature. 25 Introducing a slightly larger para-methoxycarbonyl substituent gave 1u in 95% yield. The series of meta-halogenated benzaldehydes were moderate substrates with product yields decreasing from 96% to 79% for 1h-1j as the halogen size increased from fluorine to bromine.…”

Section: Template For Synthesis Thiemementioning

confidence: 99%

Biocatalytic Synthesis of α,β-Unsaturated 2-Keto Acids and Derivatives Using the Promiscuous Aldolase, NahE

et al. 2022

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Type I aldolases catalyze carbon-carbon bond-forming reactions to form a diverse set of products in nature but often display high selectivity for their natural substrates. One such aldolase, NahE, is known to catalyze the condensation of pyruvate with a wide range of aldehydes to give trans-4-phenyl-2-oxo-3-butenoic acids under mild aqeuous conditions. These ,-unsaturated 2-oxo acids are versatile intermediates for synthetic transformations. NahE has also been used for the synthesis of α-fluoro-β-hydroxy esters, β-hydroxy esters, and quinaldic acids. However, a thorough study of the substrate scope on a practical scale has not been performed for the native NahE-catalyzed aldol condensation reaction. Here we report that NahE can accept >35 (hetero)aromatic and aliphatic aldehydes. Most condensation products derived from substituted benzaldehydes were isolated in >95% yield without need for further purification, while non-benzaldehyde substrates gave the corresponding products in isolated yields between 26 and 98%. Reactions could be performed on gram scale. These products could be converted to α,β-unsaturated carboxylic acids in up to 93% yield over two steps. This reaction sequence was also performed using whole cells in up to 79% yield. This work demonstrates that NahE is a robust, efficient, and versatile catalyst for organic synthesis.

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Section: Template For Synthesis Thiemementioning

confidence: 99%

Biocatalytic Synthesis of α,β-Unsaturated 2-Keto Acids and Derivatives Using the Promiscuous Aldolase, NahE

et al. 2022

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“…In contrast with what is described in Scheme 26, [26] in 2022 Goel and co‐workers reported a one‐pot synthesis of 3‐methylene isoindolinones 93 and related bis(isoindolinone)ethane derivatives 94 by the reacting 2‐cyanobenzaldehyde and methyl ketones 92 in the presence of KOH or K 2 CO 3 respectively (Scheme 36) reporting from low to moderate yields [36] …”

Section: Synthesis Of 3‐methylene Isoindolinonesmentioning

confidence: 91%

“…[25] In 2019 Chen and co-workers reported an efficient one-pot synthesis method for multiple heterocyclic scaffolds based on the cyano-containing amphiphilic Claisen-Schmidt reaction intermediate under basic conditions (Scheme 24). [26] Ring opening of imidate B can be ascribed to base-promoted deprotonation of the enolizable ketone.…”

Section: Introductionmentioning

confidence: 99%

Multifaceted Behavior of 2‐Cyanobenzaldehyde and 2‐Acylbenzonitriles in the Synthesis of Isoindolinones, Phthalides and Related Heterocycles

2023

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2‐Cyanobenzaldehye (also called 2‐formylbenzonitrile) and related 2‐acylbenzonitriles belong to a class of bifunctional aromatic compounds that emerged as useful starting materials in developing efficient cascade‐type reactions leading to different heterocyclic compounds. The variety of sometimes unpredictable mechanisms that rise from these structurally simple starting materials renders this class of compounds unique to afford, through divergent cascade reactions, heterocycles like isoindolinones, phthalides (also known with the name of isobenzofuranones), imidates, and in less extent isoindolin‐1‐imine, six‐ and seven‐membered heterocycles, porphyrins, also in asymmetric way exploiting different organocatalytic activation modes. To give a picture, this chemistry can be associated to Goldberg variations which stem from a common motive in a pressing and surprising way. In this Review, emphasis is also given to the synthetic methods for the access to substituted 2‐cyanobenzaldehydes and 2‐acylbenzonitriles which allowed to enlarge the scope of the described cascade reactions.

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“…Enzymes are powerful catalysts, but they are also very delicate molecules that can easily be denaturated beyond their normal environment. The application of one-step synthesis in producing polymer scaffolds has been reported in imidazole scaffolds [ 157 ], porous membrane-based scaffolds [ 158 ], multiple heterocyclic scaffolds [ 159 ], and the construction of β-Lactam scaffolds [ 160 ]. The successful fusion of enzymes with adaptable synthetic or natural polymers is made possible by a variety of opportunities provided by polymer chemistry, which can help resolve this problem.…”

Section: One-step Synthesis Applicationmentioning

confidence: 99%

Advances in the One-Step Approach of Polymeric Materials Using Enzymatic Techniques

et al. 2023

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The formulation in which biochemical enzymes are administered in polymer science plays a key role in retaining their catalytic activity. The one-step synthesis of polymers with highly sequence-controlled enzymes is a strategy employed to provide enzymes with higher catalytic activity and thermostability in material sustainability. Enzyme-catalyzed chain growth polymerization reactions using activated monomers, protein–polymer complexation techniques, covalent and non-covalent interaction, and electrostatic interactions can provide means to develop formulations that maintain the stability of the enzyme during complex material processes. Multifarious applications of catalytic enzymes are usually attributed to their efficiency, pH, and temperature, thus, progressing with a critical structure-controlled synthesis of polymer materials. Due to the obvious economics of manufacturing and environmental sustainability, the green synthesis of enzyme-catalyzed materials has attracted significant interest. Several enzymes from microorganisms and plants via enzyme-mediated material synthesis have provided a viable alternative for the appropriate synthesis of polymers, effectively utilizing the one-step approach. This review analyzes more and deeper strategies and material technologies widely used in multi-enzyme cascade platforms for engineering polymer materials, as well as their potential industrial applications, to provide an update on current trends and gaps in the one-step synthesis of materials using catalytic enzymes.

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Controlled One‐Pot Synthesis of Multiple Heterocyclic Scaffolds Based on an Amphiphilic Claisen‐Schmidt Reaction Intermediate

Cited by 8 publications

References 70 publications

Biocatalytic Synthesis of α,β-Unsaturated 2-Keto Acids and Derivatives Using the Promiscuous Aldolase, NahE

Biocatalytic Synthesis of α,β-Unsaturated 2-Keto Acids and Derivatives Using the Promiscuous Aldolase, NahE

Multifaceted Behavior of 2‐Cyanobenzaldehyde and 2‐Acylbenzonitriles in the Synthesis of Isoindolinones, Phthalides and Related Heterocycles

Advances in the One-Step Approach of Polymeric Materials Using Enzymatic Techniques

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