67385-07-3Relevant academic research and scientific papers
One-Pot Deoxygenation and Substitution of Alcohols Mediated by Sulfuryl Fluoride
Epifanov, Maxim,Mo, Jia Yi,Dubois, Rudy,Yu, Hao,Sammis, Glenn M.
supporting information, p. 3768 - 3777 (2021/03/01)
Sulfuryl fluoride is a valuable reagent for the one-pot activation and derivatization of aliphatic alcohols, but the highly reactive alkyl fluorosulfate intermediates limit both the types of reactions that can be accessed as well as the scope. Herein, we report the SO2F2-mediated alcohol substitution and deoxygenation method that relies on the conversion of fluorosulfates to alkyl halide intermediates. This strategy allows the expansion of SO2F2-mediated one-pot processes to include radical reactions, where the alkyl halides can also be exploited in the one-pot deoxygenation of primary alcohols under mild conditions (52-95% yield). This strategy can also enhance the scope of substitutions to nucleophiles that are previously incompatible with one-pot SO2F2-mediated alcohol activation and enables substitution of primary and secondary alcohols in 54-95% yield. Chiral secondary alcohols undergo a highly stereospecific (90-98% ee) double nucleophilic displacement with an overall retention of configuration.
Copper-Catalyzed Stereospecific C-S Coupling Reaction of Enantioenriched Tertiary Benzylic Amines via in Situ Activation with Methyl Triflate
Jiang, Wenlong,Li, Nutao,Zhou, Lihong,Zeng, Qingle
, p. 9899 - 9906 (2018/10/15)
A one-pot protocol for the synthesis of highly enantiopure benzylic thioethers, thioacetates, and sulfones (94-99% ee) via a ligand-free, copper-catalyzed stereospecific C-S coupling reaction of thiols and enantioenriched tertiary benzylic amines via in situ activation by methyl triflate is developed. Various enantioenriched tertiary benzylic amines, including 1-arylalkylamines, 1-tetrahydronaphthylethylamine, heterocyclic amines (e.g., 1-(thiophen-2-yl)ethanamine), and amino acid esters containing a benzylamine moiety, are highly efficient substrates, and their chirality is efficiently transferred to the products (94-99% ee). The absolute configurations of the products are predictable and follow the pattern of SN2-type substitutions; an inversion of the absolute configuration of the tertiary amines occurs during the C-S coupling reaction. Not only are various alkene-, arene-, and heteroarenethiols suitable for this C-S coupling reaction but also potassium thioacetate and sodium phenylsulfinate are as well. A plausible mechanism was proposed on the basis of the experimental results.
Ligand dependence of the synthetic approach and chiroptical properties of a magic cluster protected with a bicyclic chiral thiolate
Knoppe, Stefan,Kothalawala, Nuwan,Jupally, Vijay Reddy,Dass, Amala,Buergi, Thomas
supporting information; experimental part, p. 4630 - 4632 (2012/06/15)
Chiral gold clusters stabilised by enantiopure thiolates were prepared, size-selected and characterised by circular dichroism and mass spectrometry. The product distribution is found to be ligand dependent. Au25 clusters protected with camphorthiol show clear resemblance of their chiroptical properties with their glutathionate analogue. The Royal Society of Chemistry 2012.
Enantioselective synthesis of tertiary thiols by intramolecular arylation of lithiated thiocarbamates
MacLellan, Paul,Clayden, Jonathan
supporting information; experimental part, p. 3395 - 3397 (2011/05/04)
Lithiation of N-aryl S-α-alkylbenzyl thiocarbamates leads to rearrangement with migration of the N-aryl ring to the anionic centre α to S, a process which generally proceeds with ca. 98% retention of stereochemistry and returns chiral benzylic tertiary thiols in high enantiomeric ratios.
Palladium-catalyzed cross-coupling of benzyl thioacetates and aryl halides
Wager, Krista M.,Daniels, Matthew H.
supporting information; experimental part, p. 4052 - 4055 (2011/10/02)
A method for preparing benzyl aryl thioethers utilizing an in situ deprotection of benzyl thioacetates as an alternative to free thiols as starting materials has been developed and optimized. Good to excellent yields of diverse benzyl aryl thioethers are
KINETIC RESOLUTION
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Page/Page column 19-20, (2011/06/26)
Whilst methodologies for the Kinetic Resolution of alcohols are well established, no analogous direct methods exist for the highly selective, direct catalytic Kinetic Resolution of thiols (i.e., R-SH). The present invention relates to a method for resolving stereoisomeric mixtures of thiols. In particular, the present invention relates to purely organocatalytic mediated resolution of enantiomeric mixtures of thiols without the need for enzymes. Also disclosed are some novel catalysts. Such catalysts may comprise a cinchona alkaloid-derived moiety.
A convenient method for the preparation of alkyl aryl sulfides from alcohols and (chloromethylene)dimethylammonium chloride
Kawano, Yoshikazu,Kaneko, Nobuya,Mukaiyama, Teruaki
, p. 1612 - 1613 (2007/10/03)
(Chloromethylene)dimethylammonium chloride (Vilsmeier reagent), prepared easily from DMF and oxalyl chloride, works as an efficient condensation reagent for the thioetherification of alcohols in one-pot under mild conditions. Various alcohols are successively converted into the corresponding sulfides with inversion of configurations in moderate to high yields. Copyright
A Convenient Synthesis of Thioacetates and Thiobenzoates Using Silica-Gel Supported Potassium Thioacetate
Aoyama, Tadashi,Takido, Toshio,Kodomari, Mitsuo
, p. 3817 - 3824 (2007/10/03)
A simple and efficient procedure has been developed for the synthesis of thioesters by a reaction of alkyl halides with silica-gel supported potassium thioacetate or thiobenzoate under mild conditions.
Flavour and fragrance compositions
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, (2008/06/13)
Flavour and fragrance compositions comprising 1-mercapto-1-arylalkanes or derivatives thereof.
The configurational stability of an enantioenriched α-thiobenzyllithium derivative and the stereochemical course of its electrophilic substitution reactions; synthesis of enantiomerically pure, tertiary benzylic thiols
Stratmann, Oliver,Kaiser, Bernd,Frohlich, Roland,Meyer, Oliver,Hoppe, Dieter
, p. 423 - 435 (2007/10/03)
The lithium compound (S)-7, formed by deprotonation of the (S)-S-1-phenylethyl thiocarbamate (S)-10, is configurationally stable at -70°C. Even at elevated temperatures it racemizes only very slowly. It represents the first essentially enantiopure αthioca
