A Complete Catalytic Cycle for Supramolecular Methanol‐to‐Olefins Conversion by Linking Theory with Experiment

McCann, D. M.; Lesthaeghe, David; Kletnieks, Philip W.; Guenther, Darryl R.; Hayman, Miranda J.; Speybroeck, Véronique Van; Waroquier, Michel; Haw, James F.

doi:10.1002/ange.200705453

Cited by 78 publications

(79 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In both of the two routes, carbenium ions are involved and act as the important intermediates to produce olefins. [10][11][12][13][14][15] Specifically, the paring mechanism involves the contraction of six-membered ring cations (polymethylbenzenium cations) and the expansion of five-membered ring cations (polymethylcyclopentenyl cations). In contrast, the side-chain methylation route proceeds via the methanol methylation on polymethylbenzenium cations and subsequent elimination of side-chain groups to produce olefins.…”

mentioning

confidence: 99%

Direct Observation of Cyclic Carbenium Ions and Their Role in the Catalytic Cycle of the Methanol‐to‐Olefin Reaction over Chabazite Zeolites

et al. 2013

View full text Add to dashboard Cite

show abstract

mentioning

confidence: 99%

Direct Observation of Cyclic Carbenium Ions and Their Role in the Catalytic Cycle of the Methanol‐to‐Olefin Reaction over Chabazite Zeolites

et al. 2013

View full text Add to dashboard Cite

show abstract

“…ethanol is industrially produced from synthetic gas-derived olefins and alkanes (1)(2)(3)(4)(5)(6)(7). These reactions typically involve high temperatures and pressures that require large capital investment (8,9).…”

mentioning

confidence: 99%

Building carbon–carbon bonds using a biocatalytic methanol condensation cycle

Bogorad

Chen²,

Theisen

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

118

View full text Add to dashboard Cite

Methanol is an important intermediate in the utilization of natural gas for synthesizing other feedstock chemicals. Typically, chemical approaches for building C-C bonds from methanol require high temperature and pressure. Biological conversion of methanol to longer carbon chain compounds is feasible; however, the natural biological pathways for methanol utilization involve carbon dioxide loss or ATP expenditure. Here we demonstrated a biocatalytic pathway, termed the methanol condensation cycle (MCC), by combining the nonoxidative glycolysis with the ribulose monophosphate pathway to convert methanol to higher-chain alcohols or other acetyl-CoA derivatives using enzymatic reactions in a carbonconserved and ATP-independent system. We investigated the robustness of MCC and identified operational regions. We confirmed that the pathway forms a catalytic cycle through 13 C-carbon labeling. With a cell-free system, we demonstrated the conversion of methanol to ethanol or n-butanol. The high carbon efficiency and low operating temperature are attractive for transforming natural gas-derived methanol to longer-chain liquid fuels and other chemical derivatives.ethanol is industrially produced from synthetic gas-derived olefins and alkanes (1-7). These reactions typically involve high temperatures and pressures that require large capital investment (8, 9). The condensation of methanol to higher-chain alcohols such as ethanol or n-butanol is thermodynamically favorable (ΔG°′ = −68 and −182 kJ/mol, respectively), but the direct condensation of methanol to higher-chain alcohols has been quite challenging. Using the Guerbet reaction, methanol can upgrade short alcohols (such as n-propanol) to longer alcohols; however, methanol cannot self-couple (10). Metal acetylides can convert methanol to isobutanol, although this process was demonstrated to be noncatalytic (11).Nature has evolved several distinct ways to assimilate methanol to form metabolites necessary for growth. In principle, metabolites resulting from these methylotrophic pathways can be used to form higher-chain alcohols, although inherent pathway limitations prevent complete carbon conservation (Fig. S1). In the ribulose monophosphate pathway (RuMP), three formaldehydes condense to pyruvate, which is decarboxylated to form acetyl-CoA and CO 2 , reducing the carbon efficiency to 67%. The serine pathway requires an external supply of ATP to drive otherwise unfavorable reactions. Similarly, oxidation of methanol to CO 2 followed by CO 2 fixation using the Calvin-Benson-Bassham (CBB) cycle also requires additional ATP. To generate the required ATP input, extra carbon must be spent to drive oxidative phosphorylation. To our knowledge, natural methylotrophs are not capable of using the reductive acetyl-CoA pathway, which can produce acetyl-CoA without carbon loss or ATP requirement through carbon reassimilation after complete oxidation of methanol. This route is extremely oxygen sensitive and difficult to engineer due to the complex cofactors involved, and achieving carbo...

show abstract

“…The fundamental study of MTO or MTG process in the past 30 years produced at least 20 different mechanisms, such as oxonium ylide, carbene, carbocationic, free radical, and hydrocarbon pool [46][47][48][49]. There are undoubtedly many parallels between the reactions of methyl halides and methanol transformation to higher hydrocarbons.…”

Section: Mechanism Investigation: C-c Band Formation From Methyl Halidementioning

confidence: 99%

“…Earlier studies suggested the first C-C bond formation from methyl halide through the methylation of framework bonded CH 2 group [27][28][29][30], while later work over SAPO-34 indicated methyl halide conversion to higher hydrocarbons possibly followed indirect way as methanol conversion [49][50][51].…”

Section: Mechanism Investigation: C-c Band Formation From Methyl Halidementioning

confidence: 99%

Methyl Halide to Olefins and Gasoline over Zeolites and SAPO Catalysts: A New Route of MTO and MTG

Wei

Zhang

Liu

et al. 2012

Chinese Journal of Catalysis

View full text Add to dashboard Cite

A Complete Catalytic Cycle for Supramolecular Methanol‐to‐Olefins Conversion by Linking Theory with Experiment

Cited by 78 publications

References 33 publications

Direct Observation of Cyclic Carbenium Ions and Their Role in the Catalytic Cycle of the Methanol‐to‐Olefin Reaction over Chabazite Zeolites

Direct Observation of Cyclic Carbenium Ions and Their Role in the Catalytic Cycle of the Methanol‐to‐Olefin Reaction over Chabazite Zeolites

Building carbon–carbon bonds using a biocatalytic methanol condensation cycle

Methyl Halide to Olefins and Gasoline over Zeolites and SAPO Catalysts: A New Route of MTO and MTG

Contact Info

Product

Resources

About