Pummerer rearrangements using chlorotrimethylsilane

Lane, Simon I. R.; QUICK, S. J.; Taylor, Richard J. K.

doi:10.1016/s0040-4039(01)80094-0

Cited by 20 publications

(2 citation statements)

References 8 publications

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“…These harsh conditions usually covalently modify or degrade proteins. Trimethylchlorosilane (TMSCl) was an intriguing alternative to acetic anhydride or trifluoroacetic anhydride, particularly as TMSCl has been used as a cleavage and deprotection reagent in peptide synthesis and would be expected to cause minimal protein decomposition. In addition, TMSCl is often used for transient protection of sensitive groups, as it readily forms adducts with hydroxy groups or amines that are spontaneously removed during aqueous workup .…”

Section: Resultsmentioning

confidence: 99%

Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

et al. 2019

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The reversible oxidation of methionine residues in proteins has emerged as a biologically important post‐translational modification. However, detection and quantitation of methionine sulfoxide in proteins is difficult. Our aim is to develop a method for specifically derivatizing methionine sulfoxide residues. We report a Pummerer rearrangement of methionine sulfoxide treated sequentially with trimethylsilyl chloride and then 2‐mercaptoimidazole or pyridine‐2‐thiol to produce a dithioacetal product. This derivative is stable to standard mass spectrometry conditions, and its formation identified oxidized methionine residues. The scope and requirements of dithioacetal formation are reported for methionine sulfoxide and model substrates. The reaction intermediates have been investigated by computational techniques and by 13C NMR spectroscopy. These provide evidence for an α‐chlorinated intermediate. The derivatization allows for detection and quantitation of methionine sulfoxide in proteins by mass spectrometry and potentially by immunochemical methods.

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Section: Resultsmentioning

confidence: 99%

Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

et al. 2019

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“…In this case, the substrate or the electrophilic reagent possesses labile Si7X bonds due to which the reactions often proceed under milder conditions (generally at below-zero temperatures). Trimethylchlorosilane 54 or other silicon-containing electrophiles are used as silylating agents.…”

Section: All Three Main Experimental Versions Of This Reaction Are Em...mentioning

confidence: 99%

Rearrangements of sulfoxides and sulfones in the total synthesis of natural compounds

Prilezhaeva¹

2001

Russ. Chem. Rev.

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AbsbaCL An alomcdly ordered PdCu&o.p hydride was spthesizcd at 600 K and a hydxogcn p m s m of 3 GPa Irs Netd lanice had B primitive temgonal cell fomcd from the initial K c cell of thc disordcred PdCu alloy due to ordcrbg of the Pd and Cu atoms into allemve la)cn perpendicul;lr to the tetragonal c-ais. Rietveld refinemcat of Ihe neumn diffraction pallem of P d C u b 9 m a u r e d ai 80 K showcd thc H ~o m s to occupy octahedral interstitials within thc Pd layers. The inclastic neumu scanering sNdy at 35 K revealed a broad hydrogen o p i d peak with pcculivlties at energy m s f c n of 79 and 95 meV and of I13 meV uhich wcre zcribed to the H vibrations in the P d H planes and dong thc CU-H chains perpendiculv to the planer, respectively. The paantid for hydmgen *OM in the PdCK+9 ordered phase was thus noticeably diffcrenc even in the Pd-H plane, from that in the h o u n hydrides of pdhdium and palladium alloys. The value of approximly 116 meV was predicted forthc l o d H vibntions in dilute Cu-H solid solutions. E G 1991 Physica B 174 25741 Sov. Phys.-Solid State 33 87-90 Calcu&fions: User Manual (IFF KFA, Jiilich) Jiil-Spa-366 Rev. B 36 8798-801 A I, Bashkin IO, Sinicyn V V and Ponyatovskii E G 1989 Physlca C 162-164 1369-70 Belushkin A V 1993 Phys. Solid Srate 35 99-103

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ThePeterson Olefination Reaction

Ager¹

1990

Organic Reactions

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The Peterson olefination reaction provides a useful method for the preparation of alkenes from α‐silyl carbanions and carbonyl compounds. As alkenes hold a pivotal role in synthetic methodology for the introduction of vicinal functionality, particularly in a stereoselective manner, the Peterson reaction is increasing in importance in the reaction repertoire. This chapter discusses the reaction and its advantages over comparable methods such as the Wittig reaction. Although elimination of β‐silylalkoxides, was noted in 1947, it was not until Peterson described the preparation of functionalized alkenes from α‐silyl carbanions in 1968 that the full potential of the reaction became apparent. Alkenes are usually only isolated directly from the condensation when an anion‐stabilizing group is present in the carbanion; if not, the β‐hydroxysilane is formed. Many examples of the formation of alkenes from β‐hydroxysilanes are cited in the literature. These eliminations are discussed in this chapter, although they strictly should not be called Peterson olefination reactions. However, the “common” organic reactions of β‐hydroxysilanes which follow the usual pathways—such as the thermolytic elimination of esters derived from those alcohols—are omitted. The central nature of the Peterson reaction to organosilicon chemistry has led all reviews in this area to discuss the subject to some extent. In addition, the reaction itself has been reviewed previously.

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Pummerer rearrangements using chlorotrimethylsilane

Cited by 20 publications

References 8 publications

Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

Repurposing the Pummerer Rearrangement: Determination of Methionine Sulfoxides in Peptides

Rearrangements of sulfoxides and sulfones in the total synthesis of natural compounds

ThePeterson Olefination Reaction

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