Oxidative Fragmentations of 2-(Trimethylsilyl)ethyl Sulfoxides − Routes to Alkane-, Arene-, and Highly Substituted 1-Alkenesulfinyl Chlorides

Schwan, Adrian L.; Strickler, Rick R.; Dunn-Dufault, Robert; Brillon, Denis

doi:10.1002/1099-0690(200105)2001:9<1643::aid-ejoc1643>3.3.co;2-d

Cited by 6 publications

(10 citation statements)

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“…Both these synthetic strategies are well documented in the literature. However, since the preparation of alkanesulfinyl chlorides can be nontrivial,26 it was decided to pursue the former approach. Furthermore, the over‐oxidation product of 2 , the thiolsulfonate 3 , was also a desirable target for biological testing.…”

Section: Synthesis Of Targets and Preliminary Resultsmentioning

confidence: 99%

Thiolsulfinate Allicin from Garlic: Inspiration for a New Antimicrobial Agent

Hunter

Caira

Stellenboom

2005

Annals of the New York Academy of Sciences

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Consideration of the underlying features responsible for garlic-allicin's antimicrobial activity as well as its instability has prompted an investigation into substituted S-aryl alkylthiolsulfinates as a class of garlic mimic with enhanced stability. Synthesis of the targets has inspired the development of new methods for synthesizing unsymmetrical aralkyl disulfides, which are then oxidized to the targets. Some simple representatives have been synthesized, setting the scene for a full SAR study of this relatively unexplored class of thiolsulfinate.

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Section: Synthesis Of Targets and Preliminary Resultsmentioning

confidence: 99%

Thiolsulfinate Allicin from Garlic: Inspiration for a New Antimicrobial Agent

Hunter

Caira

Stellenboom

2005

Annals of the New York Academy of Sciences

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“…As indicated for the analytical production of 9a and 10a, PMB, DPM [14] or 2-trimethylsilylethyl [12] sulfoxides, stirring in CH 2 Cl 2 or CDCl 3 , were subjected to SO 2 Cl 2 treatment at −78 • C. After warming, the CDCl 3 solutions were analyzed directly on a Bruker Avance spectrometer operating at either 400 or 600 MHz for 1 H NMR acquisitions. CH 2 Cl 2 solutions were concentrated under dry conditions and the residue taken up in CDCl 3 for analysis.…”

Section: General Procedures For Acquisition Of Sulfinyl Chloride Nmr Datamentioning

confidence: 99%

“…Sulfinyl chloride and sulfinate ester functional groups are part of modern investigations [9,10] and, as such, double bonded compounds bearing these substituents are of interest to us [11][12][13][14][15][16] and to others [17][18][19][20][21][22][23][24][25][26][27]. Unfortunately the alkene additivity rule is unavailable for investigators in this area due to the lack of appropriate substituent constants.…”

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confidence: 99%

Determination of theZ¹H NMR chemical shift substituent parameters for the sulfinyl chloride and sulfinate ester functionalities

O’Donnell¹,

Faragher²,

Motto³

et al. 2004

Journal of Sulfur Chemistry

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Using established and new 1 H NMR data for sulfinate esters and sulfinyl chlorides, the parameters required for predicting position-dependent alkene 1 H NMR chemical shifts of vinylic sulfinate esters and vinylic sulfinyl chlorides have been obtained. Standard deviations of the new Z parameters lie in the range 0.08 to 0.15 ppm. Sulfinyl chloride and cyclohexyl sulfinate derivatives of (E) and (Z )-2-cyanoethenesulfinic acids have been prepared for the first time.The alkene additivity chemical shift rule Eq. (1) has long been used by organic chemists to interpret 1 H NMR spectra [1][2][3][4]. When a double bond configuration is uncertain, application of the rule, using tabulated chemical shift influences of substituents (Z values) usually allows a rapid and tentative, if not unequivocal, assignment of double bond geometry.Since its introduction [1], the table of substituent constants for common alkene substituents has found its way into several organic spectroscopy reference books. However, such entries are usually a reproduction of the original work [2-4], despite the emergence of new Z parameters for less common functional groups [5][6][7][8].Sulfinyl chloride and sulfinate ester functional groups are part of modern investigations [9, 10] and, as such, double bonded compounds bearing these substituents are of interest to us [11][12][13][14][15][16] and to others [17][18][19][20][21][22][23][24][25][26][27]. Unfortunately the alkene additivity rule is unavailable for investigators in this area due to the lack of appropriate substituent constants.

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“…2-(Trimethylsilyl)ethyl sulfides 2 can be prepared by free radical addition of thiols to vinyltrimethylsilane (1) (Scheme 1). [10][11][12][13][14] The addition of thiols to unsaturated compounds is a classical free radical reaction. 15 For unsaturated silanes, it has been demonstrated that silicon stabilises the free radical.…”

Section: Synthesis Of 2-(trimethylsilyl)ethanethiol and Derivativesmentioning

confidence: 99%

“…Alkyl and aryl 2-(trimethylsilyl)ethyl sulfoxides 134 prepared by oxidation of the corresponding sulfides with sodium periodate can undergo 'abnormal Pummerer type rearrangement' with clean C-S bond cleavage in the presence of sulfuryl chloride to afford sulfinyl chlorides 135 in good to excellent yields (Scheme 37). 10,14,75 This reaction was applied to the preparation of highly substituted 1alkenesulfinyl chlorides from 1-alkenyl sulfoxides. 14,75 In less substituted 1-alkene sulfoxides, reactions involving chlorination of the double bond were observed.…”

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confidence: 99%

The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

Chambert¹,

Désiré²,

Décout³

2002

Synthesis

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The trimethylsilylethyl sulfur group present in 2-(trimethylsilyl)ethyl sulfides, sulfones, sulfoxides and in 2-(trimethylsilyl)ethylsulfonamido derivatives has proved its potential in synthesis. Presence of sulfur and silicon on adjacent carbon atoms provides routes for preparing interesting sulfur or non-sulfur, silicon or non-silicon derivatives like thiols, methyl disulfides, thioesters, thiocyanates, unsaturated derivatives and amines through the selective removal of the trimethylsilylethyl or the trimethylsilyl group. 5 Conclusion

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Oxidative Fragmentations of 2-(Trimethylsilyl)ethyl Sulfoxides − Routes to Alkane-, Arene-, and Highly Substituted 1-Alkenesulfinyl Chlorides

Cited by 6 publications

References 0 publications

Thiolsulfinate Allicin from Garlic: Inspiration for a New Antimicrobial Agent

Thiolsulfinate Allicin from Garlic: Inspiration for a New Antimicrobial Agent

Determination of theZ¹H NMR chemical shift substituent parameters for the sulfinyl chloride and sulfinate ester functionalities

The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

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Oxidative Fragmentations of 2-(Trimethylsilyl)ethyl Sulfoxides − Routes to Alkane-, Arene-, and Highly Substituted 1-Alkenesulfinyl Chlorides

Cited by 6 publications

References 0 publications

Thiolsulfinate Allicin from Garlic: Inspiration for a New Antimicrobial Agent

Thiolsulfinate Allicin from Garlic: Inspiration for a New Antimicrobial Agent

Determination of theZ1H NMR chemical shift substituent parameters for the sulfinyl chloride and sulfinate ester functionalities

The 2-(Trimethylsilyl)ethyl Sulfur Group in Synthesis

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Determination of theZ¹H NMR chemical shift substituent parameters for the sulfinyl chloride and sulfinate ester functionalities