- Sulfonimidates: Useful Synthetic Intermediates for Sulfoximine Synthesis via C-S Bond Formation
-
Medicinally relevant sulfoximines are accessed from C-S coupling of sulfonimidates and commercially available organomagnesium reagents. Sulfonimidates are conveniently synthesized by oxidative alkoxylation of readily available sulfinamides. This constitutes a general C-S coupling approach for the synthesis of sulfoximines.
- Matos, Priscilla Mendon?a,Lewis, William,Moore, Jonathan C.,Stockman, Robert A.
-
p. 3674 - 3677
(2018/06/26)
-
- Tert-Butyl Sulfoxide as a Starting Point for the Synthesis of Sulfinyl Containing Compounds
-
Sulfoxides bearing a tert-butyl group can be activated using N-bromosuccinimide (NBS) under acidic conditions and then subsequently treated with a variety of nitrogen, carbon, or oxygen nucleophiles to afford a wide range of the corresponding sulfinic acid amides, new sulfoxides, and sulfinic acid esters.
- Wei, Juhong,Sun, Zhihua
-
supporting information
p. 5396 - 5399
(2015/11/18)
-
- Methyl sulfinates as electrophiles in friedel-crafts reactions. Synthesis of aryl sulfoxides
-
The Friedel-Crafts reaction of methyl alkyl- and arylsulfinates with aromatic systems, activated by one or more electron-donating substituents (OH, OMe, NHR, NR2), provides alkyl aryl and diaryl sulfoxides under mild conditions and in moderate to good yields. The very high regioselectivity usually observed in these sulfinylation reactions is rationalized on the basis of a Wheland intermediate having a trigonal bypyramidal structure in which steric and electronic interactions are significant factors strongly destabilizing the attack to the ortho positions.
- Yuste, Francisco,Hernandez Linares, Angelica,Mastranzo, Virginia M.,Ortiz, Benjamin,Sanchez-Obregon, Ruben,Fraile, Alberto,Garcia Ruano, Jose Luis
-
experimental part
p. 4635 - 4644
(2011/07/29)
-
- Mild and general method for the synthesis of sulfonamides
-
Reaction of methyl sulfinates with lithium amides followed by 3-chloroperoxybenzoic acid oxidation of the resulting sulfinamides provides primary, secondary, and tertiary alkane-, arene-and heteroarenesulfonamides in high yields. This constitutes a mild and facile experimental protocol that avoids the use of hazardous, unstable, or volatile reagents and does not affect the configurational stability of the amines. Georg Thieme Verlag Stuttgart.
- Garcia Ruano, Jose Luis,Parra, Alejandro,Yuste, Francisco,Mastranzo, Virginia M.
-
p. 311 - 319
(2008/12/22)
-
- Expedient synthesis of sulfinamides from sulfonyl chlorides
-
Sulfinamides were synthesized from sulfonyl chlorides using a procedure involving in situ reduction of sulfonyl chlorides. The reaction is broad in scope and easy to perform.
- Harmata, Michael,Zheng, Pinguan,Huang, Chaofeng,Gomes, Maria G.,Ying, Weijiang,Ranyanil, Kanok-On,Balan, Gayatri,Calkins, Nathan L.
-
p. 683 - 685
(2007/10/03)
-
- N-Hydroxy sulfonimidamides as new nitroxyl (HNO) donors
-
Chlorination and condensation of simple sulfinamides with O-benzyl and O-tert-butyl dimethyl siloxy hydroxylamine gives O-protected N-hydroxy sulfonimidamides. Deprotection of these compounds produces the corresponding sulfinamide and nitrous oxide, which
- Pennington, Richard L.,Sha, Xin,King, S. Bruce
-
p. 2331 - 2334
(2007/10/03)
-
- Effects of sulfenyl, sulfinyl and sulfonyl groups on acidities and homolytic bond dissociation energies of adjacent C-H and N-H bonds
-
Acidities and bond dissociation energies (BDEs) of the N-H bond in two phenylsulfenylamides, PhSNHBz and PhSNH-t-Bu, and four phenylsulfenylanilides, 4-GC6H4NHSPh, where G = MeO, H, Br and CN, were measured in order to compare the effects of substituents on acidities and BDEs of N-H bonds with those of C-H bonds. The effects of PhS groups on acidities and BDEs in a series of C-H acids were found to be comparable to those on acidities and BDEs of PhS in a similar series of N-H acids. Comparisons were also made of the effects of changing the oxidation state of sulfur in the series PhS, PhSO and PhSO2 on the acidities and BDEs of adjacent N-H and C-H bonds in weak acids. Hammett-type plots of PKHA values for phenyl benzyl sulfones (4-GC6H4CH2SO2Ph) and phenylsulfenylanilides (4-GC6H4NHSPh) were linear vs σp-values. A linear plot was obtained and explained for a plot of BDE of the N-H bonds in remotely substituted phenylsulfonylanilides with σ+ values. Plots of BDEs vs Eox(A-) were also linear for 4-substituted phenylsulfenylanilides (4-GC6H4NHSPh), phenylsulfonylanilides (4-GC6H4NHSO2Ph) and phenyl benzyl sulfones (4-GC6H4CH2SO2Ph).
- Bordwell, Frederick G.,Liu, Wei-Zhong
-
p. 397 - 406
(2007/10/03)
-
- Substituted N-aryl alk-1-enesulfinamides: Preparation, properties and conversion into the corresponding indole compounds [1]
-
Reaction of vinylic organometallic derivatives with N-sulfinyl arenamines 2 affords the title sulfinamides 3. On heating their solutions in selected solvents to 80-124 °C, these sulfinamides are converted into the corresponding indoles 6, probably via a [3.3]-sigmatropic rearrangement to intermediates VIII which undergo an intramolecular carbophilic reaction of the nitrogen atom with the neighboring sulfine group, followed by elimination of HSOH. The triethyloxonium tetrafluoroborate- or boron trifluoride etherate catalyzed conversion 3 → 6 can be carried out at a much lower temperature. Elsevier,.
- Baudin, Jean-Bernard,Commenil, Marie-Gabrielle,Julia, Sylvestre A.,Lorne, Robert,Mauclaire, Laurent
-
p. 329 - 350
(2007/10/03)
-
- ON THE MECHANISM OF THE REACTION OF NITROSOBENZENES WITH BENZENETHIOL: THE INTERMEDIACY OF AMINOXYLS AND THEIR DEOXYGENATION
-
The reaction of benzenethiol with several substituted nitrosobenzenes carried out inside the cavity of an EPR spectrometer evidences the formation of adducts through the detection of the corresponding thionitroxides.The macroscale reaction of benzenethiol with nitrosobenzene confirmed the formation of the adduct and clarified the nature of the intermediates.The formation of azoxybenzene, aniline and nitrobenzene shows that an electron-transfer process between nitrosobenzene and benzenethiol is in competition with nucleophylic addition of the latter to the former compound.The identification of S-phenylbenzenethiosulphinate as well as the isolation of compound 9, bearing a sulphinyl group on a benzene ring, implies the formation of a sulphinyl radical, which is considered to be responsible for the formation of the sulphinylamide.The formation of the sulpheneamide, the main reaction product, is attributed to the interaction of thiyl radicals with the intermediate thionitroxides.The crystal structure of S-methyl-S-phenyl-N-(o-sulphonylphenyl)benzenesulphilimine, the unexpected product of the methylation of compound 9, is also described.
- Alberti, Angelo,Benaglia, Massimo,Carloni, Patricia,Greci, Lucedio,Stipa, Pierluigi,et al.
-
p. 555 - 562
(2007/10/02)
-
- SULFENAMIDES AND SULFINAMIDES V. CONJUGATIVE AFFINITY AND pKa VALUES OF ARYL SULFINAMIDES
-
pKa values and NMR properties of aryl sulfinamides are discussed with respect to conjugative affinity in the sulfinamido group. - Key words: Sulfinamides; pKa values; conjugative affinity, NMR, spectrophotometry.
- Clarke, Victor,Cole, Edward R.
-
p. 243 - 248
(2007/10/02)
-
- Reaction of Benzenesulfinyl Azide with Thiols and Amines. Preparation of Thiosulfinates and Sulfinamides
-
Reaction of benzenesulfinyl azide (1) with thiols at -20 deg C gave thiosulfinates and hydrazoic acid.Reaction of 1 with primary and secondary amines gave sulfinamides and hydrazoic acid.The presence of a hydroxyl group in the thiol or amine did not change the course of the reaction.Thus, a thiosulfinate and sulfinamide containing a free hydroxyl group could be prepared.Yields ranging from 41percent to 93percent were obtained.
- Maricich, Tom J.,Angeletakis, Christos N.
-
p. 1931 - 1934
(2007/10/02)
-
- Chlorinolyses of Alkyl (or Aryl) Phtalimidomethyl Sulfides with Sulfuryl Chloride or Chlorine in the Presence and the Absence of Acetic Acid
-
Alkyl and aryl phtalimidomethyl sulfides give alkane- and arenesulfenyl chlorides on reaction with equimolar sulfuryl chloride or molecular chlorine in an aprotic solvent at room temperature, but give alkene- and arenesulfinyl chlorides on reaction with two molar equivalents of the same reagent in the presence of acetic anhydride under the same conditions.The utility of these reactions for the synthesis of organo sulfenyl chlorides and sulfinyl chlorides was confirmed.Keywords- chlorinolysis; oxidative cleavage; alkyl (or aryl) phtalimidomethyl sulfide; alkane (or arene) sulfinyl chloride; 2-chloro-alkyl sulfides; α,β-unsaturated sulfides
- Uchino, Makoto,Sekiya, Minoru
-
p. 126 - 133
(2007/10/02)
-