41719-04-4Relevant academic research and scientific papers
Sulfinamide Synthesis Using Organometallic Reagents, DABSO, and Amines
Lo, Pui Kin Tony,Oliver, Gwyndaf A.,Willis, Michael C.
, p. 5753 - 5760 (2020/04/30)
We report the synthesis of sulfinamides using organometallic reagents, a sulfur dioxide reagent, and nitrogen based-nucleophiles. The addition of an organometallic reagent to the commercially available sulfur dioxide surrogate, DABSO, generates a metal sulfinate which is reacted with thionyl chloride to form a sulfinyl chloride intermediate. Trapping the sulfinyl chlorides in situ with a variety of nitrogen nucleophiles delivers sulfinamides in 32-83% yields. Each stage of the process is performed at room temperature, and the total reaction time is only 1.5 h.
A New, Practical One-Pot Synthesis of Unprotected Sulfonimidamides by Transfer of Electrophilic NH to Sulfinamides
Izzo, Flavia,Sch?fer, Martina,Stockman, Robert,Lücking, Ulrich
supporting information, p. 15189 - 15193 (2017/10/12)
Unprotected tertiary sulfonimidamides have been prepared in good to excellent yields in a one-pot transformation from tertiary sulfinamides through NH transfer. The reaction is mediated by commercially available (diacetoxyiodo)benzene and ammonium carbamate in methanol under convenient conditions. A wide range of functional groups are tolerated and initial results indicate that the NH transfer is stereospecific. A small molecule X-ray analysis of NH sulfonimidamide 2 a and its behavior in selected in vitro assays in comparison to the matched sulfonamide are also reported. This new reaction provides a safe, short and efficient approach to sulfonimidamides, which have been the subject of recent, growing interest in the life sciences.
Enantioselective synthesis of an atropisomeric diaryl ether
Clayden, Jonathan,Worrall, Christopher P.,Moran, Wesley J.,Helliwell, Madeleine
supporting information; experimental part, p. 3234 - 3237 (2009/02/08)
(Chemical Equation Presented) Twisted ethers: Introduction of a bulky alkylsulfinyl substituent ortho to the C-O axis of a diaryl ether imposes a powerful conformational preference (see scheme). The preference persists upon oxidation of the sulfoxide to a sulfone, leading to dynamic thermodynamic resolution of the atropisomeric ether. This is the first enantioselective synthesis of an atropisomeric diaryl ether not forming part of a macrocyclic ring.
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
, p. 1643 - 1654 (2007/10/03)
The preparation of a collection of alkyl, aryl, and 1-alkenyl 2-(trimethylsilyl)ethyl sulfoxides is outlined, using mostly vinyltrimethylsilane or 2-(trimethylsilyl)ethanesulfenyl chloride (5) as key starting materials. The 2-(trimethylsilyl)ethyl group can be cleaved from many of the sulfoxides under oxidative fragmentation conditions using sulfuryl chloride and the reaction represents a new protocol for sulfinyl chloride synthesis. The method is suitable for most alkane- and arenesulfinyl chlorides (3), but is limited to highly substituted vinylic sulfinyl chlorides. 1-Alkenyl 2-(trimethylsilyl)ethyl sulfoxides with reduced double bond substitution (6, 7, 11) succumb to reactions involving chlorination of the double bond. The β-effect of silicon is invoked to explain the ability of the 2-(trimethylsilyl)ethyl group to induce C-S bond scission under the oxidative cleavage reaction conditions. A mechanism is offered to account for the role played by the β-silicon atom of the 2-(trimethylsilyl)ethyl group. Indeed, the silicon atom is self-sacrificial in that it diverts the course of the reaction from the usual α-carbon chlorination mode to one of oxidative cleavage, whereby the 2-(trimethylsilyl)ethyl group is lost. The overall reaction calls upon the ability of silicon atoms to donate electron density by hyperconjugation.
The reaction of 2-trimethylsilylethyl sulfoxides with sulfuryl chloride. A fragmentation route to sulfinyl chlorides
Schwan,Dufault
, p. 3973 - 3974 (2007/10/02)
Sulfinyl chlorides were prepared in good to excellent yields by reacting aryl or alkyl 2-trimethylsilylethyl sulfoxides with SO2Cl2.
Chlorinolyses of Alkyl (or Aryl) Phtalimidomethyl Sulfides with Sulfuryl Chloride or Chlorine in the Presence and the Absence of Acetic Acid
Uchino, Makoto,Sekiya, Minoru
, p. 126 - 133 (2007/10/02)
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
