Insertion of .gamma.-SO3 into Perfluoroalkyl- and Polyfluoroalkoxysilanes

Holfter, H.; Kirchmeier, Robert L.; Shreeve, Jean’ne M.

doi:10.1021/ic00104a055

Cited by 12 publications

(6 citation statements)

References 5 publications

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“…All silanes except 2,2,2-trifluoroethoxytrimethylsilane were commercially obtained (Aldrich, Milwaukee, WI). A lab sample of 2,2,2-trifluoroethoxytrimethylsilane was prepared as described by Kirchmeier and co-workers [68].…”

Section: Methodsmentioning

confidence: 99%

Fluorotrimethylsilane affinities of anionic nucleophiles: A study of fluoride-induced desilylation

Krouse

Wenthold

2005

J. Am. Soc. Mass Spectrom.

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In this study, preparation and decomposition of five novel pentavalent fluorosiliconates, RSi(CH 3 ) 3 F Ϫ (R ϭ CH 3 CH 2 O, CF 3 CH 2 O, (CH 3 ) 2 CHO, (CH 3 ) 3 SiO, and (CH 3 ) 3 SiNH) is used to investigate the process of fluoride-induced desilylation. The siliconates were characterized by collision-induced dissociation and energy-resolved mass spectrometry. Decomposition of RSi(CH 3 ) 3 F Ϫ leads to loss of the nucleophile R Ϫ and FSi(CH 3 ) 3 , except in the case of (CH 3 ) 3 SiNHSi(CH 3 ) 3 F Ϫ , where HF loss is also observed. Ion affinities for FSi(CH 3 ) 3 have been measured for all five nucleophiles, and compare well with computational predictions. The observed trend of the bond dissociation energies resembles the trend of ⌬H acid values for the corresponding conjugate acids, RH. Additionally, this data has been incorporated with existing thermochemistry to derive fluoride affinities for four of the silanes (R ϭ CH 3 CH 2 O, (CH 3 ) 2 CHO, (CH 3 ) 3 SiO, and (CH 3 ) 3 SiNH). We use the fluoride affinity of the silanes and the FSi(CH 3 ) 3 affinity of the departing nucleophilic anion to assess the feasibility of fluorideinduced desilylation of the silanes examined in this work. (J Am Soc Mass Spectrom 2005, 16, 697-707)

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Section: Methodsmentioning

confidence: 99%

Fluorotrimethylsilane affinities of anionic nucleophiles: A study of fluoride-induced desilylation

Krouse

Wenthold

2005

J. Am. Soc. Mass Spectrom.

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“…Sulfur-based electrophiles that contain highly reactive S−X (X = F, Cl) bond are readily pentafluorophenylated giving valuable substitution products (Scheme ) . Similar to trifluoromethylation of sulfimides, pentafluorophenylation can be carried out under mild conditions.…”

Section: 33 Perfluoroarylationmentioning

confidence: 99%

“…Compound 2 mildly reacts with γ-SO 3 giving the product of a formal insertion of the SO 3 unit into the Si-CF 3 bond of 2. 85 This transformation permits the preparation of trimethylsilylated derivative of synthetically useful triflic acid in one step (eq 41).…”

Section: Sulfur-based Electrophilesmentioning

confidence: 99%

Perfluoroalkylation with Organosilicon Reagents

1997

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in the Chemistry Department at USC in the tenure track. He was promoted to full professorship in 1994. Currently, he holds the Olah Nobel Laureate Chair in Hydrocarbon Chemistry with research contributions and interests in new fluorination methods, new synthetic methods, mechanistic studies of organic reactions, electrochemistry, and superacid and hydrocarbon chemistry. He has published more than 300 papers, book chapters, and review articles; coauthored 4 books; and holds 3 patents. He has received many honors and recognition. He is currently an Advisory Editor of the International Journal of Porphyrins and Pthalocyanins.

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“…Indeed, there is only one reported example of the process of this type, the interaction of Me 3 SiCF 3 with sulfur trioxide leading to Me 3 SiOTf through the insertion of SO 3 into C-Si bond [5].…”

Section: Introductionmentioning

confidence: 99%