Formaldehyde as<scp>C</scp>1 Synthon in Organic Synthesis

Li, Wanfang; Wu, Xiao‐Feng

doi:10.1002/9783527831883.ch5

Cited by 5 publications

(2 citation statements)

References 298 publications

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“…There is an increasing interest in the use of formaldehyde as a C1 feedstock (Desmons et al, 2019; W. Li & Wu, 2022), given the ease with which it can be derived from biomass or CO 2 and the versatility with which it can be upgraded to value‐added products. The value of formaldehyde as a C1 synthon in organic synthesis is well established (W. Li & Wu, 2015; Meninno & Lattanzi, 2016), primarily due to its reactivity and versatility in C–C bond formation as well as for chiral synthesis.…”

Section: Introductionmentioning

confidence: 99%

Development of a kinetic model and figures of merit for formaldehyde carboligations catalyzed by formolase enzymes

Massad

Banta

2022

Biotech & Bioengineering

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There is an increasing interest in the upgrading of inexpensive and abundant C1 feedstocks to higher carbon products. Linear carbon ligation routes are of particular interest due to their simplicity and potential for high carbon efficiencies. The formolase (FLS) enzyme was computationally designed to catalyze the formose reaction, where formaldehyde molecules are coupled to produce a mixture of C2 (glycolaldehyde) and C3 (dihydroxyacetone) molecules. Recent protein engineering efforts have resulted in the introduction of several FLS variants with altered catalytic properties. As is often the case with enzymes catalyzing reactions with complex and/or nonnatural trajectories, there are no mechanistic kinetic models that fully describe the activity of the FLS enzyme. FLS variants are typically evaluated by fitting rate data to empirical rate laws, with some variation of the kcat/KM ratio used to report and rank performances. The apparent parameters estimated in this manner are unlikely to capture the full catalytic performance of these enzymes. In this study, we derive a mechanistic rate law describing FLS activity as well as theory‐based figures of merit to rank FLS performance under relevant conditions. We proceed to fit the rate equation to initial rate data obtained from several FLS mutants, and use the figures of merit to compare the mutations. This study provides a theoretical framework for comparing FLS enzymes which will be essential as novel carbon ligation pathways are devised and implemented.

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Section: Introductionmentioning

confidence: 99%

Development of a kinetic model and figures of merit for formaldehyde carboligations catalyzed by formolase enzymes

Massad

Banta

2022

Biotech & Bioengineering

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“…The asymmetric cross-aldol reaction with formaldehyde, also known as enantioselective hydroxymethylation or methylolation, is one of the most efficient carbon chain extension methods, which is greatly rewarding in terms of atom economy and gaining molecular complexity. 1 Because of the gaseous, reactive, and toxic nature of anhydrous formaldehyde, performing this reaction is far from straightforward, and thus, easier-to-handle formaldehyde sources are usually engaged. However, despite their practicality, aqueous formaldehyde solutions may cause incompatibility issues with many catalytic systems due to the presence of water and methanol as a stabilizer.…”

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confidence: 99%

Asymmetric Organocatalyzed Transfer Hydroxymethylation of Isoindolinones Using Formaldehyde Surrogates

Svestka,

Bobal,

Waser

et al. 2024

Org. Lett.

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The piperidine-based Takemoto catalyst has been successfully employed in a novel asymmetric transfer hydroxymethylation of activated isoindolinones, allowing us to prepare the enantioenriched hydroxymethylated adducts in good to excellent yields (48−96%) and enantiopurities (81:19−97:3 e.r.). To increase the reaction rate without compromising the selectivity, carefully optimized formaldehyde surrogates were employed, providing a convenient source of anhydrous formaldehyde with a base-triggered release. The substrate scope, including 34 entries, showed the considerable generality of the asymmetric transformation, and most entries exhibited complete conversions in 24− 48 h. A scale-up experiment and multiple enantioselective downstream transformations were also carried out, suggesting the prospective synthetic utility of the products.

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Replacing syngas by formic acid and acetic anhydride with advantages: tandem carbonylation of renewable terpenes and propenylbenzenes

Delolo,

Moreira,

de O. Dias

et al. 2024

Journal of Catalysis

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Formaldehyde asC1 Synthon in Organic Synthesis

Cited by 5 publications

References 298 publications

Development of a kinetic model and figures of merit for formaldehyde carboligations catalyzed by formolase enzymes

Development of a kinetic model and figures of merit for formaldehyde carboligations catalyzed by formolase enzymes

Asymmetric Organocatalyzed Transfer Hydroxymethylation of Isoindolinones Using Formaldehyde Surrogates

Replacing syngas by formic acid and acetic anhydride with advantages: tandem carbonylation of renewable terpenes and propenylbenzenes

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