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.

A one-pot cascade transformation of ketones into α-imidoketones has been developed, in which N-bromosuccinimide (NBS) provides both electrophilic bromine and nucleophilic nitrogen sources, and diazabicyclo[5.4.1]undec-7-ene (DBU) functions as a base and a nucleophilic promoter for the activation of NBS. α-Bromination is supposed as the key step in the process, which takes place between more electrophilic bromide active species and enolates.

[1]  Cui,et al.  Mechanistic evaluation of the halocyclization of 4-penten-1-ol by some Bis(2-substituted pyridine) and Bis(2,6-disubstituted pyridine)bromonium triflates , 2000, The Journal of organic chemistry.

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

[3]  M. C. Feiters,et al.  Commemorating two centuries of iodine research: an interdisciplinary overview of current research. , 2011, Angewandte Chemie.

[4]  José A. Souto,et al.  Enantioselective metal-free diamination of styrenes. , 2011, Angewandte Chemie.

[5]  S. Snyder,et al.  Simple reagents for direct halonium-induced polyene cyclizations. , 2010, Journal of the American Chemical Society.

[6]  Q. Fu,et al.  Halonium-initiated electrophilic cascades of 1-alkenoylcyclopropane carboxamides: efficient access to dihydrofuropyridinones and 3(2H)-furanones. , 2011, Chemical communications.

[7]  Eduardo C. Escudero‐Adán,et al.  Metal-free diamination of alkenes employing bromide catalysis , 2012 .

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

[9]  A. Yudin,et al.  Oxidative cycloamination of olefins with aziridines as a versatile route to saturated nitrogen-containing heterocycles. , 2003, Journal of the American Chemical Society.

[10]  Feng Chen,et al.  Asymmetric bromolactonization using amino-thiocarbamate catalyst. , 2010, Journal of the American Chemical Society.

[11]  R. Srivastava,et al.  New phthalimide derivatives with potent analgesic activity: II. , 1998, Bioorganic & medicinal chemistry letters.

[12]  J. Cui,et al.  Synthesis and anti-inflammatory activity of N-phthalimidomethyl 2,3-dideoxy- and 2,3-unsaturated glycosides. , 2007, Carbohydrate research.

[13]  Sukbok Chang,et al.  Intermolecular oxidative C-N bond formation under metal-free conditions: control of chemoselectivity between aryl sp2 and benzylic sp3 C-H bond imidation. , 2011, Journal of the American Chemical Society.

[14]  V. Gevorgyan,et al.  Dual role of alkynyl halides in one-step synthesis of alkynyl epoxides. , 2008, Journal of the American Chemical Society.

[15]  K. Rissanen,et al.  Breathing molecular crystals: halogen- and hydrogen-bonded porous molecular crystals with solvent induced adaptation of the nanosized channels , 2012 .

[16]  S. Huber,et al.  Halogen-bond-induced activation of a carbon-heteroatom bond. , 2011, Angewandte Chemie.

[17]  J. Robert,et al.  New anti-inflammatory N-pyridinyl(alkyl)phthalimides acting as tumour necrosis factor-alpha production inhibitors. , 2001, European journal of medicinal chemistry.

[18]  A. Abdel-Hafez.  Synthesis and anticonvulsant evaluation ofN-substituted-isoindolinedione derivatives , 2004, Archives of pharmacal research.

[19]  S. Denmark,et al.  Lewis base catalysis of bromo- and iodolactonization, and cycloetherification , 2010, Proceedings of the National Academy of Sciences.

[20]  Brenton DeBoef,et al.  Metal-free intermolecular oxidative C-N bond formation via tandem C-H and N-H bond functionalization. , 2011, Journal of the American Chemical Society.

[21]  Lee Brammer,et al.  Supramolecular chemistry of halogens: complementary features of inorganic (M-X) and organic (C-X') halogens applied to M-X...X'-C halogen bond formation. , 2005, Journal of the American Chemical Society.

[22]  K. Miyamoto,et al.  Highly Regioselective Amination of Unactivated Alkanes by Hypervalent Sulfonylimino-λ3-Bromane , 2011, Science.

[23]  K. Muñiz,et al.  An approach to the regioselective diamination of conjugated di- and trienes. , 2012, Chemistry.

[24]  A. Córdova,et al.  Organocatalytic enantioselective aminosulfenylation of alpha,beta-unsaturated aldehydes. , 2008, Angewandte Chemie.

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

[26]  M. Haghdadi,et al.  Bis‐Bromine‐1,4‐Diazabicyclo[2.2.2]Octane (Br2‐DABCO) as an Efficient Promoter for One‐Pot Conversion of N‐Arylglycines to N‐Arylsydnones in the Presence of NaNO2/Ac2O Under Neutral Conditions , 2008 .

[27]  Neeraj Kumar,et al.  Recent advances in the chemistry of phthalimide analogues and their therapeutic potential. , 2010, Mini reviews in medicinal chemistry.

[28]  J. C. Martin,et al.  The Identity of the Chain-Carrying Species in Brominations with N-Bromosuccinimide: Selectivity of Substituted N-Bromosuccinimides toward Substituted Toluenes , 1963 .

[29]  P. Stang,et al.  Chemistry of polyvalent iodine. , 2008, Chemical reviews.

[30]  Pierangelo Metrangolo,et al.  Halogen bonding in supramolecular chemistry. , 2008, Angewandte Chemie.

[31]  J. Vaquero,et al.  Reaction of imines with N-iodosuccinimide (NIS): unexpected formation of stable 1 : 1 complexes. , 2007, Chemical communications.

[32]  David J. Williams,et al.  X-Ray and SCF–MO model study of the complex formed between N-bromosuccinimide and 1,4-diazabicyclo[2.2.2]octane , 1984 .

[33]  Benhur Godoi,et al.  Synthesis of heterocycles via electrophilic cyclization of alkynes containing heteroatom. , 2011, Chemical reviews.

[34]  L. M. Lima,et al.  Synthesis and anti-inflammatory activity of phthalimide derivatives, designed as new thalidomide analogues. , 2002, Bioorganic & medicinal chemistry.

[35]  Xumu Zhang,et al.  Highly enantioselective asymmetric hydrogenation of alpha-phthalimide ketone: an efficient entry to enantiomerically pure amino alcohols. , 2004, Journal of the American Chemical Society.

[36]  Hua Fu,et al.  Copper-catalyzed coupling of tertiary aliphatic amines with terminal alkynes to propargylamines via C-H activation. , 2008, The Journal of organic chemistry.

[37]  H. Chuman,et al.  A new type of imido group donor: synthesis and characterization of sulfonylimino-lambda(3)-bromane that acts as a nitrenoid in the aziridination of olefins at room temperature under metal-free conditions. , 2007, Journal of the American Chemical Society.

[38]  José A. Souto,et al.  Iodine(III)-mediated intermolecular allylic amination under metal-free conditions. , 2012, Journal of the American Chemical Society.

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

[40]  K. Tanemura,et al.  Halogenation of Aromatic Compounds by N-chloro-, N-bromo-, and N-iodosuccinimide , 2003 .

[41]  Pascal Retailleau,et al.  Highly enantioselective electrophilic α-bromination of enecarbamates: chiral phosphoric acid and calcium phosphate salt catalysts. , 2012, Journal of the American Chemical Society.

[42]  C. Walling,et al.  Positive Halogen Compounds. VIII. Structure and Reactivity in N-Bromosuccinimide Brominations , 1963 .

[43]  A. Lei,et al.  Bond formations between two nucleophiles: transition metal catalyzed oxidative cross-coupling reactions. , 2011, Chemical reviews.

[44]  E. P. Burrows,et al.  Rimocidin. I. Carbon skeleton, partial structure, and absolute configuration at C-27. , 1965, Journal of the American Chemical Society.

[45]  Scott A Snyder,et al.  Et2SBrSbCl5Br: an effective reagent for direct bromonium-induced polyene cyclizations. , 2009, Angewandte Chemie.

[46]  F. Liang,et al.  Halonium-initiated C-O bond formation via umpolung of α-carbon to the carbonyl: efficient access to 5-amino-3(2H)-furanones. , 2012, Organic letters.

[47]  A. Sakakura,et al.  Enantioselective halocyclization of polyprenoids induced by nucleophilic phosphoramidites , 2007, Nature.

[48]  Xiaoming Feng,et al.  Catalytic asymmetric bromoamination of chalcones: highly efficient synthesis of chiral alpha-bromo-beta-amino ketone derivatives. , 2010, Angewandte Chemie.

[49]  V. Gevorgyan,et al.  Double duty for cyanogen bromide in a cascade synthesis of cyanoepoxides. , 2011, Angewandte Chemie.

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

[51]  Glen A. Russell,et al.  Directive Effects in Aliphatic Substitutions. XIX. Photobromination with N-Bromosuccinimide , 1963 .

[52]  L. Horner,et al.  Neuere Methoden der präparativen organischen Chemie II 14. N-Bromsuccinimid, Eigenschaften und Reaktionsweisen Studien zum Ablauf der Substitution XV† , 1959 .