Abstract Molecular design ultimately furnishes improvements in performance over time, and this has been the case for Rh‐ and Ir‐based molecular catalysts currently used in transfer hydrogenation (TH) reactions for fine chemical synthesis. In this report, we describe a molecular pincer ligand Al catalyst for TH, (I2P2−)Al(THF)Cl (I2P=diiminopyridine; THF=tetrahydrofuran). The mechanism for TH is initiated by two successive Al‐ligand cooperative bond activations of the O−H bonds in two molecules of isopropanol (iPrOH) to afford six‐coordinate (H2I2P)Al(OiPr)2Cl. Stoichiometric chemical reactions and kinetic experiments suggest an ordered transition state, supported by polar solvents, for concerted hydride transfer fromiPrO−to substrate. Metal‐ligand cooperative hydrogen bonding in a cyclic transition state is a likely support for the concerted hydride transfer event. The available data does not support involvement of an intermediate Al‐hydride in the TH. Proof‐of‐principle reactions including the conversion of isopropanol and benzophenone to acetone and diphenylmethanol with 90 % conversion in 1 h are described. The analogous hydride compound, (I2P2−)Al(THF)H, also cleaves the O−H bond iniPrOH to afford (HI2P−)Al(OiPr)H and (HI2P−)Al(OiPr)2, but no activity for catalytic TH was observed.
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Genome-scale flux balance analysis reveals redox trade-offs in the metabolism of the thermoacidophile Methylacidiphilum fumariolicum under auto-, hetero-and methanotrophic conditions
Members of the genusMethylacidiphilumare thermoacidophile methanotrophs with optimal growth temperatures between 50°C and 60°C, and pH between 1.0 and 3.0. These microorganisms, as well as other extremophile bacteria, offer an attractive platform for environmental and industrial biotechnology because of their robust operating conditions and capacity to grow using low-cost substrates. In this study, we isolatedMethylacidiphilum fumariolicumstr. Pic from a crater lake located in the state of Chiapas, Mexico. We sequenced the genome and built a genome-scale metabolic model. The manually curated model contains 667 metabolites, 729 reactions, and 473 genes. Predicted flux distributions using flux balance analysis identified changes in redox trade-offs under methanotrophic and autotrophic conditions (H2+CO2). This was also predicted under heterotrophic conditions (acetone, isopropanol, and propane). Model validation was performed by testing the capacity of the strains to grow using four substrates: CH4, acetone, isopropanol, and LP-Gas. The results suggest that the metabolism ofM. fumariolicumstr. Pic is limited by the regeneration of redox equivalents such as NAD(P)H and reduced cytochromes.
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- Award ID(s):
- 2313313
- PAR ID:
- 10533102
- Editor(s):
- Rodrigue, Agnès
- Publisher / Repository:
- Frontiers
- Date Published:
- Journal Name:
- Frontiers in Systems Biology
- Edition / Version:
- 1
- Volume:
- 4
- Issue:
- 1
- ISSN:
- 2674-0702
- Page Range / eLocation ID:
- 1-18
- Subject(s) / Keyword(s):
- verrucomicrobia, thermoacidophile, methanotroph, genome-scale metabolic model, flux balance analysis
- Format(s):
- Medium: X Size: 2MB Other: xls
- Size(s):
- 2MB
- Sponsoring Org:
- National Science Foundation
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