Methyltrifluoromethanesulfonate

Alder, Roger W.; Phillips, Justin G. E.; Huang, Lijun; Huang, Xuefei

doi:10.1002/047084289x.rm266m.pub2

Cited by 7 publications

(7 citation statements)

References 122 publications

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“…A spectroscopically silent methyl donor is necessary to trap and characterize the products of methyl transfer to M121A Ni I Az. Due to rapid hydrolysis of methyl triflate in aqueous solution, , which precludes reaction with M121A Ni I Az (Figure S2), methyl iodide was again selected as a methylating agent for spectroscopic studies on Ni-CH 3 Az species, despite the potential for multiple reaction pathways.…”

Section: Resultsmentioning

confidence: 99%

A Biochemical Nickel(I) State Supports Nucleophilic Alkyl Addition: A Roadmap for Methyl Reactivity in Acetyl Coenzyme A Synthase

et al. 2019

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Nickel-containing enzymes such as methyl coenzyme M reductase (MCR) and carbon monoxide dehydrogenase/acetyl coenzyme A synthase (CODH/ACS) play a critical role in global energy conversion reactions, with significant contributions to carbon-centered processes. These enzymes are implied to cycle through a series of nickel-based organometallic intermediates during catalysis, though identification of these intermediates remains challenging. In this work, we have developed and characterized a nickel-containing metalloprotein that models the methyl-bound organometallic intermediates proposed in the native enzymes. Using a nickel(I)-substituted azurin mutant, we demonstrate that alkyl binding occurs via nucleophilic addition of methyl iodide as a methyl donor. The paramagnetic NiIII-CH3 species initially generated can be rapidly reduced to a high-spin NiII-CH3 species in the presence of exogenous reducing agent, following a reaction sequence analogous to that proposed for ACS. These two distinct bioorganometallic species have been characterized by optical, EPR, XAS, and MCD spectroscopy, and the overall mechanism describing methyl reactivity with nickel azurin has been quantitatively modeled using global kinetic simulations. A comparison between the nickel azurin protein system and existing ACS model compounds is presented. NiIII-CH3 Az is only the second example of two-electron addition of methyl iodide to a NiI center to give an isolable species and the first to be formed in a biologically relevant system. These results highlight the divergent reactivity of nickel across the two intermediates, with implications for likely reaction mechanisms and catalytically relevant states in the native ACS enzyme.

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Section: Resultsmentioning

confidence: 99%

A Biochemical Nickel(I) State Supports Nucleophilic Alkyl Addition: A Roadmap for Methyl Reactivity in Acetyl Coenzyme A Synthase

et al. 2019

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“…The polymerization mechanism of THF with this initiator is known to follow the so-called “active chain end” (ACE) mechanism (Scheme ) regarding the polymerization of CEO, in accordance to literature describing the polymerization of THF . The commonly very powerful methylating agent MeOTf methylates the ring system either of THF or CEO to enable the following nucleophilic attack of the oxygen atom at another cyclic monomer. This step can be repeated either with CEO or THF monomers, leading to linear chains.…”

Section: Resultsmentioning

confidence: 67%

Poly(THF-co-cyano ethylene oxide): Cyano Ethylene Oxide (CEO) Copolymerization with THF Leading to Multifunctional and Water-Soluble PolyTHF Polyelectrolytes

et al. 2016

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Cyano-functional polyether copolymers based on THF were prepared via cationic ring-opening copolymerization of THF with cyano ethylene oxide (CEO). The CEO content of poly(tetrahydrofuran) (polyTHF) based copolymers varied from 3.3 to 29.3%, and molecular weights ranged from 5100 to 31900 g•mol −1 with M w /M n in the range of 1.31 to 1.74 (SEC in THF, PS standards). The polymerization was conducted with methyl trifluoromethanesulfonate (MeOTf) as an initiator. Kinetic studies concerning incorporation of both monomers were performed via NMR spectroscopy. The cyano groups at the poly(THF-co-CEO) copolymers enable direct access to amino (polyTHF−NH 2 ) and carboxyl groups (polyTHF−COOH) in facile one-step procedures, respectively. The modified copolymers were characterized via NMR, MALDI−ToF mass, and FT-IR spectroscopy. Thermal properties of the materials were studied via differential scanning calorimetry (DSC), demonstrating a gradual decrease of the melting points with increasing amount of CEO in the copolymers (from 30 °C for 3.3% CEO to 21 °C for 8.4% CEO). After postmodification to carboxylic acid groups the melting points decrease from 26 to 18 °C in the series of copolymers. Contact angles of water on thin films of the polymers can be tuned in a wide range from 72.7°to 17.8°by varying the CEO fraction as well as by postmodification. Crystallization studies of CaCO 3 with water-soluble polyTHF−COOH revealed the composition-dependent inhibition of calcite growth, with crystallite size in the mineralization process being controlled by the amount of carboxylic acid groups at the poly(THF) copolymers.

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“…Having successfully utilized methyl trifluoromethanesulfonate in the Figure >1.0 kg synthesis of lipid 2 with an HPLC purity of >99.8%, we wished to demonstrate that the concentration of potentially mutagenic methyl trifluoromethanesulfonate-related materials, with a daily allowed regulatory threshold of 1.5 μg/day, was below the 1.5 ppm level for a 1.0 g daily dose . We viewed the high reactivity of methyl trifluoromethanesulfonate, reported to be up to 10 4 greater than methyl iodide, as suggestive that it would not survive the synthesis of 2 . We thought it unlikely that methyl trifluoromethanesulfonate would survive the washing and extraction of 2 into MeOH-10% aq.…”

Section: Results and Discussionmentioning

confidence: 99%

Development of a Safe and Scalable Process for the Production of a High-Purity Thiocarbamate-Based Ionizable Lipid as an Excipient in mRNA-Encapsulating Lipid Nanoparticles

Rajappan

Tanis

Roberts

et al. 2021

Org. Process Res. Dev.

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Thiocarbamate lipid 2 was prepared on a 25–50 g scale by coupling a carbamoyl chloride with 3-(dimethylamino)-1-propanethiol. Chromatography, activated charcoal treatment, and washing were required to obtain 2 (57%, light yellow oil) in >98% purity. Lipid 2 was successfully prepared on a 1 kg scale by replacing the carbamoyl chloride with an acyl imidazolium intermediate and coupling with the lipophilic amine salt 8 to give 2 in a higher yield (68%) and greater purity (99.8%, colorless oil) using an improved, chromatography-free, purification protocol. In addition, mutagenic impurities in 2 could be controlled well below required specifications.

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Methyltrifluoromethanesulfonate

Cited by 7 publications

References 122 publications

A Biochemical Nickel(I) State Supports Nucleophilic Alkyl Addition: A Roadmap for Methyl Reactivity in Acetyl Coenzyme A Synthase

A Biochemical Nickel(I) State Supports Nucleophilic Alkyl Addition: A Roadmap for Methyl Reactivity in Acetyl Coenzyme A Synthase

Poly(THF-co-cyano ethylene oxide): Cyano Ethylene Oxide (CEO) Copolymerization with THF Leading to Multifunctional and Water-Soluble PolyTHF Polyelectrolytes

Development of a Safe and Scalable Process for the Production of a High-Purity Thiocarbamate-Based Ionizable Lipid as an Excipient in mRNA-Encapsulating Lipid Nanoparticles

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