An unprecedented synthesis of γ-lactams via mercaptoacetylation of aziridines in water

A highly green and expeditious route to α-mercapto-γ-lactams from masked mercapto acids viz. 2-phenyl-2-methyl-1,3-oxathiolan-5-ones, and tosyl aziridines in an excellent yield (82–93%) is reported. The synthetic protocol involves regioselective opening of the terminal aziridine ring and mercaptoacetylative cyclisation cascades in a one-pot procedure wherein water acts as both a catalyst as well as a solvent. These reactions were carried out in aqueous media as well as under solvent-free conditions, however, under solvent-free conditions, lower yields are obtained.

[1]  Santosh K. Singh,et al.  Nucleophilic acylation of α-haloketones with aldehydes: an umpolung strategy for the synthesis of 1,3-diketones , 2011 .

[2]  Jinhua Liu,et al.  Synthesis of pyrrolidin-2-ones via tandem reactions of vinyl sulfonium salts under mild conditions , 2010 .

[3]  Garima,et al.  The first example of ring expansion of N-tosylaziridines to 2-aroyl-N-tosylazetidines with nitrogen ylides in an aqueous medium , 2010 .

[4]  P. Lu.  Recent Developments in Regioselective Ring Opening of Aziridines , 2010 .

[5]  G. Fabrizi,et al.  Diastereoselective synthesis of hexahydro-3H-pyrrolyzin-3-ones through Pd-catalyzed carboamination. , 2010, The Journal of organic chemistry.

[6]  D. Dixon,et al.  Total synthesis of (-)-nakadomarin A. , 2009, Journal of the American Chemical Society.

[7]  Dan‐Wei Zhang,et al.  Synthesis of gamma-butyrolactams by photoinduced PhSe group transfer radical cyclization and formal synthesis of (+/-)-isocynometrine with diphenyldiselenide as promoter. , 2009, The Journal of organic chemistry.

[8]  B. Malawska,et al.  Design, synthesis and pharmacological evaluation of new 1-[3-(4-arylpiperazin-1-yl)-2-hydroxy-propyl]-3,3-diphenylpyrrolidin-2-one derivatives with antiarrhythmic, antihypertensive, and alpha-adrenolytic activity. , 2009, European journal of medicinal chemistry.

[9]  D. Dixon,et al.  Nitro-Mannich/lactamization cascades for the direct stereoselective synthesis of pyrrolidin-2-ones. , 2009, Organic letters.

[10]  R. B. Nazarski,et al.  Cyclisation at very high temperature. Thermal transformations of N-alkyl and N, N-dialkyl amides of α,β-unsaturated acids into mono- and bicyclic heterocycles under FVT conditions , 2009 .

[11]  Santosh K. Singh,et al.  Catalyst-free, step and pot economic, efficient mercaptoacetylative cyclisation in H2O: synthesis of 3-mercaptocoumarins , 2009 .

[12]  C. Kouklovsky,et al.  Amino acid homologation by the Blaise reaction: a new entry into nitrogen heterocycles. , 2009, The Journal of organic chemistry.

[13]  D. Hall,et al.  Diversity-oriented synthesis and preliminary biological screening of highly substituted five-membered lactones and lactams originating from an allyboration of aldehydes and imines. , 2009, Journal of combinatorial chemistry.

[14]  Victor W. Pike,et al.  Synthesis, ex vivo evaluation, and radiolabeling of potent 1,5-diphenylpyrrolidin-2-one cannabinoid subtype-1 receptor ligands as candidates for in vivo imaging. , 2008, Journal of medicinal chemistry.

[15]  A. Meden,et al.  One-pot parallel solution-phase synthesis of 1-substituted 4-(2-aminoethyl)-1H-pyrazol-5-ols. , 2008, Journal of combinatorial chemistry.

[16]  W. Wolf,et al.  A convenient synthesis and cytotoxic evaluation of N-unsubstituted α-methylene-γ-lactams , 2008 .

[17]  De‐Xian Wang,et al.  Reversal of nucleophilicity of enamides in water: control of cyclization pathways by reaction media for the orthogonal synthesis of dihydropyridinone and pyrrolidinone Clausena alkaloids. , 2008, Organic letters.

[18]  Yong Cui,et al.  Hot water-promoted ring-opening of epoxides and aziridines by water and other nucleopliles. , 2008, The Journal of organic chemistry.

[19]  Xiao‐Ming Li,et al.  Highly brominated mono- and bis-phenols from the marine red alga Symphyocladia latiuscula with radical-scavenging activity. , 2007, Journal of natural products.

[20]  N. Mani,et al.  High-Yielding Syntheses of 1-Piperidin-4-yl Butyro- and Valerolactams through a Tandem Reductive Amination−Lactamization (Reductive Lactamization) , 2007 .

[21]  Vijai K. Rai,et al.  One-pot dehydrazinative β-glycosylation in aqueous media : Synthesis of benzoxazinone C-nucleosides , 2007 .

[22]  S. Minakata,et al.  Ring opening and expansion of aziridines in a silica-water reaction medium. , 2006, The Journal of organic chemistry.

[23]  P. Ferruti,et al.  New Stimuli Responsive Poly(1-vinylpyrrolidin-2-one) Bearing Pendant Activated Disulfide Groups , 2006 .

[24]  L. Yadav,et al.  Mercaptoacetic acid based expeditious synthesis of polyfunctionalised 1,3-thiazines , 2005 .

[25]  M. Ruiz,et al.  Organocatalytic ring expansion of beta-lactams to gamma-lactams through a novel N1-C4 bond cleavage. direct synthesis of enantiopure succinimide derivatives. , 2005, Organic letters.

[26]  B. Pasternak,et al.  Cyclisation at very high temperature. Thermal transformations of N-alkyl and N,N-dialkyl cinnamic amides into pyrrolidin-2-ones under FVT conditions , 2005 .

[27]  C. Santana,et al.  Synthesis of 4-aryl-2-pyrrolidones and beta-aryl-gamma-amino-butyric acid (GABA) analogues by Heck arylation of 3-pyrrolines with arenediazonium tetrafluoroborates. Synthesis of (+/-)-rolipram on a multigram scale and chromatographic resolution by semipreparative chiral simulated moving bed chromato , 2005, The Journal of organic chemistry.

[28]  L. Yadav,et al.  A novel salicylaldehyde based mineral supported expedient synthesis of benzoxazinone nucleosides , 2004 .

[29]  R. Breslow.  Determining the geometries of transition States by use of antihydrophobic additives in water. , 2004, Accounts of chemical research.

[30]  J. S. Rao,et al.  Applications of Baylis–Hillman acetates: one-pot, facile and convenient synthesis of substituted γ-lactams , 2004 .

[31]  S. Minakata,et al.  Silica-water reaction media: its application to the formation and ring opening of aziridines. , 2004, Angewandte Chemie.

[32]  N. Brace.  Radical addition of RFI to alkenylsuccinic anhydrides and gem-substituted alkenyl triesters , 2003 .

[33]  B. S. Holla,et al.  New bis-aminomercaptotriazoles and bis-triazolothiadiazoles as possible anticancer agents. , 2002, European journal of medicinal chemistry.

[34]  J. Vicario,et al.  Aziridine ring-opening reactions with chiral enolates. Stereocontrolled synthesis of 5-substituted-3-methyl-pyrrolidin-2-ones. , 2001, The Journal of organic chemistry.

[35]  V. Hruby,et al.  Rational design of highly diastereoselective, organic base-catalyzed, room-temperature Michael addition reactions. , 2000, The Journal of organic chemistry.

[36]  K. Kondo,et al.  Practical synthesis of (R)-4-mercaptopyrrolidine-2-thione from L-aspartic acid. Preparation of a novel orally active 1-beta-methylcarbapenem, TA-949. , 2000, The Journal of organic chemistry.

[37]  K. Hirai,et al.  TRIALS FOR THE SYNTHESIS OF (R)-4-MERCAPTO-PYRROLIDIN-2-ONE ((R)-MPD) , 1999 .

[38]  M. Fontecave,et al.  Synthesis of 2′-thio-uridine and -cytidine derivatives as potential inhibitors of ribonucleoside diphosphate reductase: thionitrites, disulfides and 2′-thiouridine 5′-diphosphate , 1997 .

[39]  B. Kalluraya,et al.  Synthesis, characterisation and antifungal activity of some N-bridged heterocycles derived from 3-(3-bromo-4-methoxyphenyl)-4-amino-5-mercapto-1,2,4-triazole. , 1996, Farmaco.

[40]  A. Parsons.  Recent developments in kainoid amino acid chemistry , 1996 .

[41]  R. Rieke,et al.  A Facile Synthesis of .gamma.-Lactams and Secondary Amines from Conjugated Dienes and Imines , 1995 .

[42]  S. Wnuk.  Sulfur- and seleno-sugar modified nucleosides. Synthesis, chemical transformations and biological properties. , 1993 .

[43]  R. Beabealashvilli,et al.  3′‐Mercapto‐2′,3′‐dideoxynucleotides are high effective terminators of DNA synthesis catalyzed by HIV reverse transcriptase , 1992, FEBS Letters.

[44]  Ronald Breslow,et al.  Hydrophobic Effects on Simple Organic Reactions in Water , 1991 .

[45]  C. Chidester,et al.  Novel anxiolytic agents derived from alpha-amino-alpha-phenyl-o-tolyl-4H-triazoles and -imidazoles. , 1978, Journal of medicinal chemistry.

[46]  D. Wöhrle.  Polymere aus Nitrilen. II. Einige Polykondensationsreaktionen des 2.5‐Diimino‐pyrrolidins, Imino‐pyrrolidons, Succinimids, 5‐Chlor‐2‐imino‐1‐pyrrolins und Bernsteinsäuredinitrils , 1972 .

[47]  J. David,et al.  Synthesis of some s-triazoles with potential analgetic and antiinflammatory activities. , 1971, Journal of medicinal chemistry.