One-Flow Syntheses of Unsymmetrical Sulfamides and N-Substituted Sulfamate Esters.

We developed one-flow syntheses of unsymmetrical sulfamides and N-substituted sulfamate esters by changing a nucleophile and a tertiary amine from inexpensive and commercially available chlorosulfonic acid. In the synthesis of N-substituted sulfamate esters, unexpected symmetrical sulfite formation was suppressed by changing the tertiary amine. The effect of tertiary amines was proposed using linear regression. Our approach rapidly (≤90 s) provides desired products containing acidic and/or basic labile groups without tedious purification under mild (20 °C) conditions.

[1]  H. Masui,et al.  Verification of preparations of (1H-indol-3-yl)methyl electrophiles and development of their microflow rapid generation and substitution , 2023, Communications Chemistry.

[2]  R. Krems,et al.  Rapid and Mild One‐Flow Synthetic Approach to Unsymmetrical Sulfamides Guided by Bayesian Optimization , 2021, Chemistry–Methods.

[3]  X. Xie,et al.  Implementation of Diverse Synthetic and Strategic Approaches to Biologically Active Sulfamides , 2021 .

[4]  J. Pelletier,et al.  Development of sulfahydantoin derivatives as β-lactamase inhibitors. , 2021, Bioorganic & medicinal chemistry letters.

[5]  K. Nakata,et al.  Lewis Acid‐Catalyzed Nucleophilic Substitutions of Benzylic Alcohols with Sulfamides , 2020 .

[6]  J. Roizen,et al.  Photochemically-mediated nickel-catalyzed synthesis of N-(hetero)aryl sulfamides. , 2019, The Journal of organic chemistry.

[7]  Shinichiro Fuse,et al.  Single-Step, Rapid, and Mild Synthesis of β-Amino Acid N-Carboxy Anhydrides Using Micro-Flow Technology. , 2019, Chemistry, an Asian journal.

[8]  Melanie A Short,et al.  Efficient synthesis of unsymmetrical sulfamides from sulfamic acid salts by activation with triphenylphosphine ditriflate , 2019, Tetrahedron.

[9]  Shinichiro Fuse,et al.  Rapid and Mild Synthesis of Amino Acid N-Carboxy Anhydrides: Basic-to-Acidic Flash Switching in a Microflow Reactor. , 2018, Angewandte Chemie.

[10]  K. Sharpless,et al.  A New Portal to SuFEx Click Chemistry: A Stable Fluorosulfuryl Imidazolium Salt Emerging as an "F-SO2 +" Donor of Unprecedented Reactivity, Selectivity, and Scope. , 2018, Angewandte Chemie.

[11]  J. Roizen,et al.  Synthesis of N-Substituted Sulfamate Esters from Sulfamic Acid Salts by Activation with Triphenylphosphine Ditriflate. , 2017, Organic letters.

[12]  J. Marrot,et al.  Efficient Synthesis of Unsymmetrical Sulfamides via a Lossen‐Like Rearrangement , 2016 .

[13]  H. Saeidian,et al.  The first general protocol for N-monoalkylation of sulfamate esters: benign synthesis of N-alkyl Topiramate (anticonvulsant drug) derivatives , 2015 .

[14]  H. Saeidian,et al.  Synthesis and reactivity of imidazole-1-sulfonate esters (imidazylates) in substitution, elimination, and metal-catalyzed cross-coupling reactions: a review , 2015 .

[15]  Yuanfu Deng,et al.  Copper(II)-catalyzed enantioselective intramolecular cyclization of N-alkenylureas. , 2015, Organic letters.

[16]  W. J. Spillane,et al.  Sulfamic acid and its N- and O-substituted derivatives. , 2014, Chemical reviews.

[17]  Jun-ichi Yoshida,et al.  Flash chemistry: flow microreactor synthesis based on high-resolution reaction time control. , 2010, Chemical record.

[18]  J. Yoshida What is Flash Chemistry , 2008 .

[19]  Jun-ichi Yoshida,et al.  Flash chemistry: fast chemical synthesis by using microreactors. , 2008, Chemistry.

[20]  C. Supuran,et al.  Therapeutic potential of sulfamides as enzyme inhibitors , 2006, Medicinal research reviews.

[21]  A. Merschaert,et al.  Mild and safer preparative method for nonsymmetrical sulfamides via N-sulfamoyloxazolidinone derivatives: Electronic effects affect the transsulfamoylation reactivity , 2006 .

[22]  Scott D. Taylor,et al.  Introduction of 2,2,2-trichloroethyl-protected sulfates into monosaccharides with a sulfuryl imidazolium salt and application to the synthesis of sulfated carbohydrates. , 2006, Angewandte Chemie.

[23]  C. Supuran,et al.  Sulfamates and their therapeutic potential , 2005, Medicinal research reviews.

[24]  M. Nieger,et al.  Sulfamide Synthesis via Pd-Catalysed Cross-Coupling , 2004 .

[25]  S. Connon,et al.  Acrylamide in the Baylis-Hillman reaction: expanded reaction scope and the unexpected superiority of DABCO over more basic tertiary amine catalysts. , 2004, The Journal of organic chemistry.

[26]  L. Alcaraz,et al.  Novel N-aryl and N-heteroaryl sulfamide synthesis via palladium cross coupling. , 2004, Organic letters.

[27]  Luigi Cavallo,et al.  A Combined Experimental and Theoretical Study Examining the Binding of N-Heterocyclic Carbenes (NHC) to the Cp*RuCl (Cp* = η5-C5Me5) Moiety: Insight into Stereoelectronic Differences between Unsaturated and Saturated NHC Ligands , 2003 .

[28]  K. E. Kinsey,et al.  Preparation of unsymmetrical sulfonylureas from N,N'-sulfuryldiimidazoles. , 2003, The Journal of organic chemistry.

[29]  J. Winum,et al.  N-(tert-butoxycarbonyl)-N-[4-(dimethylazaniumylidene)-1,4-dihydropyridin-1-ylsulfonyl]azanide: a new sulfamyolating agent. Structure and reactivity toward amines. , 2001, Organic letters.

[30]  J. Montero,et al.  Synthesis of n-sulfamoyloxazolidinones and -perhydrooxazinones reactivity and use as donors in the transsulfamoylation reaction; application to the preparation of 2-chloroethylnitrososulfamides. IV , 1996 .

[31]  J. Montero,et al.  A new family of potential oncostatics: 2-chloroethylnitrososulfamides (CENS)--I. Synthesis, structure, and pharmacological evaluation (preliminary results). , 1996, Bioorganic & medicinal chemistry.

[32]  J. Montero,et al.  Synthesis of pseudonucleosides containing chiral sulfahydantoins as aglycone (II) , 1996 .

[33]  W. J. Spillane,et al.  A Useful, Alternative Synthesis of Unsymmetrical and Symmetrical N,N′-Disubstituted Sulfamides by Transamidatiion Reactions of Sulfamides with Amines , 1983 .

[34]  R. Stephenson,et al.  Sulfonylamine-mediated sulfamation of amines. A mild, high yield synthesis of sulfamic acid salts , 1980 .

[35]  G. DuBois Amination of aryl sulfamate esters. A convenient general synthesis of aliphatic sulfamides , 1980 .

[36]  T. Nagai,et al.  On the Behavior of Sulfonyl Imide as a Reactive Intermediate. The Reaction with Enamines , 1979 .

[37]  J. Kloek,et al.  An improved synthesis of sulfamoyl chlorides , 1976 .

[38]  G. Schulze,et al.  Herstellung und Reaktionen von N‐Monoalkyl‐amidosulfonylchloriden , 1969 .

[39]  George M. Atkins,et al.  N-Sulfonyl amines , 1967 .

[40]  H. Hall,et al.  Correlation of the Base Strengths of Amines1 , 1957 .

[41]  M. L. Bender,et al.  General Basic Catalysis of Ester Hydrolysis and Its Relationship to Enzymatic Hydrolysis1 , 1957 .

[42]  W. W. Binkley,et al.  Organic Syntheses With Sulfuryl-Chloride , 1939 .

[43]  W. J. Spillane,et al.  Versatile synthesis of sulphamate esters by phase-transfer methods , 1982 .

[44]  H. Hall Potentiometric Determination of the Base Strength of Amines in Non-protolytic Solvents , 1956 .