Divergent Synthesis of α,α‐Dihaloamides through α,α‐Dihalogenation of β‐Oxo Amides by Using N‐Halosuccinimides

An efficient and divergent one-pot synthesis of α,α-dihaloamides from readily available β-oxo amides based on the selection of reaction conditions is reported. α,α-Dihalo-β-oxo amides were produced by treating β-oxo amides with N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS) in water at room temperature, whereas α,α-dihaloacetamides were synthesized by subjecting β-oxo amides to NCS or NBS in ethanol under reflux.

[1]  K. Gholivand,et al.  Diorganotin(IV) complexes of N -mono-, di- and tri-chloroacetyl, N ′, N ″-bis(isopropyl) phosphoric triamide , 2012 .

[2]  Weiping Tang,et al.  Enantioselective bromolactonization of conjugated (Z)-enynes. , 2010, Journal of the American Chemical Society.

[3]  A. Renslo,et al.  Conformational constraint in oxazolidinone antibacterials. Synthesis and structure-activity studies of (azabicyclo[3.1.0]hexylphenyl)oxazolidinones. , 2005, Journal of medicinal chemistry.

[4]  A. Fujishima,et al.  Enhanced electrogenerated chemiluminescence of a ruthenium tris(2,2')bipyridyl/tripropylamine system on a boron-doped diamond nanograss array. , 2010, Chemical communications.

[5]  Y. Yeung,et al.  Enantioselective bromolactonization of cis-1,2-disubstituted olefinic acids using an amino-thiocarbamate catalyst. , 2012, Chemical communications.

[6]  X. Bi,et al.  Intramolecular hydrogen bonding-assisted cyclocondensation of α-diazoketones with various amines: a strategy for highly efficient Wolff 1,2,3-triazole synthesis. , 2012, Chemical communications.

[7]  Tao Chen,et al.  Efficient medium ring size bromolactonization using a sulfur-based zwitterionic organocatalyst. , 2012, Journal of the American Chemical Society.

[8]  Z. Novák,et al.  N-Halosuccinimide/SiCl4 as general, mild and efficient systems for the α-monohalogenation of carbonyl compounds and for benzylic halogenation , 2011 .

[9]  Peng-mian Huang,et al.  Lawesson's reagent-initiated domino reaction of aminopropenoyl cyclopropanes: synthesis of thieno[3,2-c]pyridinones. , 2012, Organic & biomolecular chemistry.

[10]  Jingyao Zhou,et al.  Facile, efficient, and catalyst-free electrophilic aminoalkoxylation of olefins: scope and application. , 2010, Journal of the American Chemical Society.

[11]  D. Davies,et al.  Preparation of N-Heterocycles by Radical Cyclisation of Enamides Mediated by Manganese(III) or Copper(I). A Comparison of Cyclisation Methods , 2000 .

[12]  M. Uchiyama,et al.  Radical cyclizations in 1,4-dimethylpiperazine , 2006 .

[13]  M. Bertrand,et al.  3-Oxa- and 3-Azabicyclo[3.1.0]hexan-2-ones via Tandem Radical Cyclization-Intramolecular S(N)2 Reactions. , 1996, The Journal of organic chemistry.

[14]  C. Zheng,et al.  An efficient enantioselective synthesis of florfenicol via asymmetric aziridination , 2011 .

[15]  C. Djerassi,et al.  Brominations with N-bromosuccinimide and related compounds; the Wohl-Ziegler reaction. , 1948, Chemical reviews.

[16]  Jiming Yang,et al.  Regioselective synthesis of 3-arylamino- and 5-arylaminoisoxazoles from enaminones. , 2012, Organic letters.

[17]  Cyrus O. Guss,et al.  Bromohydrins from Olefins and N-Bromosuccinimide in Water , 1955 .

[18]  O. Piermatti,et al.  Recent Advances in Lewis Acid Catalyzed Diels−Alder Reactions in Aqueous Media , 2001 .

[19]  Jingyao Zhou,et al.  Multicomponent approach in the synthesis of 2,2,6-trisubstituted morpholine derivatives. , 2012, Organic letters.

[20]  Qun Liu,et al.  A Clean, Facile and Practical Synthesis of α-Oxoketene S,S-Acetals in Water , 2006 .

[21]  I. Pravst,et al.  Directed regioselectivity of bromination of ketones with NBS: solvent-free conditions versus water , 2006 .

[22]  Fluorinated chloramphenicol acetyltransferase thermostability and activity profile: improved thermostability by a single-isoleucine mutant. , 2007, Bioorganic & medicinal chemistry letters.

[23]  K. Tanemura,et al.  A mild and efficient procedure for alpha-bromination of ketones using N-bromosuccinimide catalysed by ammonium acetate. , 2004, Chemical communications.

[24]  H. Schmid,et al.  Verbesserung und Erweiterung der Bromierungsmethode mit Brom-succinimid , 1946 .

[25]  Dan Yang,et al.  Mild α-Halogenation Reactions of 1,3-Dicarbonyl Compounds Catalyzed by Lewis Acids , 2002 .

[26]  L. Pasquato,et al.  “RS+” as a Coupling Reagent for Phosphorylation and Carboxylic Acid Activation , 2001 .

[27]  D. Schumacher,et al.  An Improved Industrial Synthesis of Florfenicol plus an Enantioselective Total Synthesis of Thiamphenicol and Florfenicol. , 1997, The Journal of organic chemistry.

[28]  A. Chappell,et al.  Reactions of Carbonyl-Conjugated Alkynes with N-Bromosuccinimide and N-Iodosuccinimide in DMF/H2O and Methanol/Sulfuric Acid: Syntheses of Dihalo Diketones, Dihalo Ketoesters, and Dihalo Acetals† , 1998 .

[29]  G. Lin,et al.  New stereoselective synthesis of thiamphenicol and florfenicol from enantiomerically pure cyanohydrin : a chemo-enzymatic approach , 2008 .

[30]  A. Butler,et al.  Vanadium bromoperoxidase from Delisea pulchra: enzyme-catalyzed formation of bromofuranone and attendant disruption of quorum sensing. , 2011, Chemical communications.

[31]  P. Yang,et al.  Novel N-phenyl dichloroacetamide derivatives as anticancer reagents: design, synthesis and biological evaluation. , 2010, European journal of medicinal chemistry.

[32]  Ikuo Fujii,et al.  Correlation between Antigen-Combining-Site Structures and Functions within a Panel of Catalytic Antibodies Generated against a Single Transition State Analog , 1995 .

[33]  R. Merényi,et al.  Chlorierung von N‐substituierten Carbonsäureamiden , 1978 .

[34]  Chao-Jun Li.  Organic reactions in aqueous media - with a focus on carbon-carbon bond formation , 1993 .

[35]  D. Schumacher,et al.  An efficient synthesis of florfenicol , 1990 .

[36]  F. Liang,et al.  One-pot cascade leading to direct α-imidation of ketones by a combination of N-bromosuccinimide and 1,8-diazabicyclo[5.4.1]undec-7-ene. , 2012, Organic letters.

[37]  Fenguo Zhou,et al.  Facile and efficient synthesis of quinolin-2(1H)-ones via cyclization of penta-2,4-dienamides mediated by H2SO4. , 2012, Organic & biomolecular chemistry.

[38]  P. Esteves,et al.  Trihaloisocyanuric acids as convenient reagents for regioselective halogenation of β-dicarbonyl compounds , 2009 .

[39]  H. Meshram,et al.  Amberlyst-15®-promoted efficient 2-halogenation of 1,3-keto-esters and cyclic ketones using N-halosuccinimides , 2005 .

[40]  Jung-Nam Park,et al.  Synthetic applications of the cyclic iminocarbonate rearrangement: enantioselective syntheses of chloramphenicol and 4-epi-cytoxazone , 2000 .

[41]  B. Staskun.  Steric inhibition to cyclization of .beta.-keto amides to indeno[1,2,3-de]quinolinones and related compounds , 1980 .

[42]  Weibing. Liu,et al.  Organic synthesis using (diacetoxyiodo)benzene (DIB): Unexpected and novel oxidation of 3-oxo-butanamides to 2,2-dihalo-N-phenylacetamides , 2012, Beilstein journal of organic chemistry.

[43]  Peng-mian Huang,et al.  Vilsmeier-type reaction of dimethylaminoalkenoyl cyclopropanes: one-pot access to 2,3-dihydrofuro [3,2-c]pyridin-4(5H)-ones. , 2012, Organic letters.

[44]  Y. Monguchi,et al.  Platinum on Carbon-Catalyzed Precise Reduction Control of Trichloromethyl to Geminal-Dichloromethyl Groups , 2012 .

[45]  M. Zupan,et al.  Visible light induced ‘on water’ benzylic bromination with N-bromosuccinimide , 2006 .

[46]  O. Prakash,et al.  Synthesis and in vitro activity of novel 1,2,4-triazolo[4,3-a]pyrimidine oxazolidinone antibacterial agents. , 2011, Bioorganic & medicinal chemistry letters.

[47]  F. Vögtle,et al.  Bromierungen mit N‐Bromsuccinimid: Solvens und Selektivität , 1980 .

[48]  K. Manabe,et al.  Development of novel Lewis acid catalysts for selective organic reactions in aqueous media. , 2002, Accounts of chemical research.

[49]  W. Herrmann,et al.  Aqueous-Phase Organometallic Catalysis: Concepts and Applications , 2005 .