A Hydrazine Insertion Route to N'-Alkyl Benzohydrazides by an Unexpected Carbon-Carbon Bond Cleavage.

A serendipitous carbon-carbon bond cleavage in the reaction of benzoyl acrylates, derived from Morita-Baylis-Hillman adducts, with hydrazines delivered new N',N'-disubstituted benzohydrazides. The reaction features a regioselective formation of two carbon-nitrogen bonds and works well with a range of acrylates and hydrazines. A brief mechanistic investigation alluded to a cyclic hemiaminal as a plausible intermediate.

[1]  K. Morita,et al.  A Tertiary Phosphine-catalyzed Reaction of Acrylic Compounds with Aldehydes , 1968 .

[2]  E. Corey,et al.  Total synthesis of gibberellic acid. A simple synthesis of a key intermediate , 1982 .

[3]  K. D. Wing,et al.  RH 5849, a Nonsteroidal Ecdysone Agonist: Effects on Larval Lepidoptera. , 1988, Science.

[4]  K. D. Wing.  RH 5849, a nonsteroidal ecdysone agonist: effects on a Drosophila cell line. , 1988, Science.

[5]  H. Hoffmann,et al.  Synthesis and reactions of .alpha.-methylene-.beta.-keto sulfones , 1991 .

[6]  U. Eggert,et al.  Preparation and Selected Reactions of t‐Butyl 2‐Methylene‐3‐oxoalkanoates , 1991 .

[7]  K. Janda,et al.  Azatides: Solution and liquid phase syntheses of a new peptidomimetic , 1996 .

[8]  M. Villani,et al.  Susceptibility of Japanese Beetle, Oriental Beetle, and European Chafer (Coleoptera: Scarabaeidae) to Halofenozide, an Insect Growth Regulator , 1996 .

[9]  G. Dujardin,et al.  (S)-(+)-3-p-Tolylsulfinylbut-3-en-2-one: A spectacular oxabutadiene for asymmetric cycloaddition of styrenic compounds , 1996 .

[10]  Reactivity of 2-Methylene-1,3-dicarbonyl Compounds. Stereoselective and Asymmetric Diels-Alder Reactions. , 1996, The Journal of organic chemistry.

[11]  M. Villani,et al.  Selective toxicity of halofenozide to exotic white grubs (Coleoptera: Scarabaeidae) , 1999 .

[12]  U. Ragnarsson.  Synthetic methodology for alkyl substituted hydrazines , 2001 .

[13]  J. B. Arterburn,et al.  Catalytic amination of 2-substituted pyridines with hydrazine derivatives. , 2001, Organic letters.

[14]  S. Buchwald,et al.  Synthesis of N-aryl hydrazides by copper-catalyzed coupling of hydrazides with aryl iodides. , 2001, Organic letters.

[15]  M. Yamauchi.  Reactivity of 2‐methylene‐1,3‐dicarbonyl compounds. 1,3‐dipolar cycloaddition reaction with nitrile oxide , 2002 .

[16]  N-Acylhydrazines: Future Perspectives Offered by New Syntheses and Chemistry , 2004 .

[17]  Jieping Zhu,et al.  The enantioselective Morita-Baylis-Hillman reaction and its aza counterpart. , 2007, Angewandte Chemie.

[18]  T. Soeta,et al.  Enantioselective Conjugate Addition of Hydrazines to α,β-Unsaturated Imides. Synthesis of Chiral Pyrazolidinones , 2007 .

[19]  Palladium-catalyzed cross-coupling between vinyl halides and tert-butyl carbazate: first general synthesis of the unusual N-Boc-N-alkenylhydrazines. , 2007, Organic letters.

[20]  Ashutosh Pratap Singh,et al.  IBX/Sc(OTf)3-promoted one-pot oxidative conjugate addition of allyltrimethylsilane to Baylis–Hillman adducts , 2007 .

[21]  The first one-pot oxidative Michael reaction of Baylis–Hillman adducts with indoles promoted by iodoxybenzoic acid , 2007 .

[22]  F. Aricò,et al.  Reaction of the ambident electrophile dimethyl carbonate with the ambident nucleophile phenylhydrazine. , 2008, The Journal of organic chemistry.

[23]  L. Yadav,et al.  Ionic liquid-promoted one-pot oxidative Michael addition of TMSCN to Baylis–Hillman adducts , 2008 .

[24]  S. Batra,et al.  Advances in the Baylis–Hillman reaction-assisted synthesis of cyclic frameworks , 2008 .

[25]  A. Chan,et al.  Copper(I)-picolinic acid catalyzed N-arylation of hydrazides , 2008 .

[26]  L. Yadav,et al.  Ionic liquid [Hmim]HSO4-promoted one-pot oxidative conjugate addition of sulfur-centred nucleophiles to Baylis-Hillman adducts , 2008 .

[27]  M. Shi,et al.  Recent extensions of the Morita-Baylis-Hillman reaction. , 2009, Chemical Communications.

[28]  L. Yadav,et al.  IBX/LiBr-promoted one-pot oxidative anti-Markownikov bromohydroxylation/bromoalkoxylation of Baylis–Hillman olefins , 2009 .

[29]  J. Barrault,et al.  Catalyst-free aqueous multicomponent domino reactions from formaldehyde and 1,3-dicarbonyl derivatives , 2009 .

[30]  L. Yadav,et al.  The first one-pot oxidative 1,2-acetoxysulfenylation and 1,2-disulfenylation of Baylis–Hillman alcohols in an ionic liquid , 2009 .

[31]  I. Dez,et al.  TBD-organocatalysed synthesis of pyrazolines. , 2009, Organic & biomolecular chemistry.

[32]  D. Basavaiah,et al.  Recent contributions from the Baylis-Hillman reaction to organic chemistry. , 2010, Chemical reviews.

[33]  Haoquan Li,et al.  Water mediated trapping of active methylene intermediates generated by IBX-induced oxidation of Baylis–Hillman adducts with nucleophiles , 2010 .

[34]  J. Cui,et al.  New class of potent antitumor acylhydrazone derivatives containing furan. , 2010, European journal of medicinal chemistry.

[35]  Jing Yang,et al.  Oxidative oxo Diels–Alder Reactions of Baylis–Hillman Adducts with Electron-Rich Alkenes in the Presence of IBX , 2012 .

[36]  F. Coelho,et al.  Oxidizing Morita-Baylis-Hillman adducts towards vicinal tricarbonyl compounds , 2012 .

[37]  Ying‐Chun Chen,et al.  Organocatalytic asymmetric transformations of modified Morita-Baylis-Hillman adducts. , 2012, Chemical Society reviews.

[38]  Yongwen Jiang,et al.  Assembly of N,N-disubstituted hydrazines and 1-aryl-1H-indazoles via copper-catalyzed coupling reactions. , 2012, Organic letters.

[39]  M. L. Vasconcellos,et al.  Morita-Baylis-Hillman adducts: biological activities and potentialities to the discovery of new cheaper drugs. , 2012, Bioorganic & medicinal chemistry.

[40]  M. Shi,et al.  Recent advances in organocatalytic asymmetric Morita-Baylis-Hillman/aza-Morita-Baylis-Hillman reactions. , 2013, Chemical reviews.

[41]  Zhengjie He,et al.  Highly chemoselective Rauhut-Currier reaction between maleimides and enones and dual phosphine-mediated one-pot synthesis of bicyclic and polycyclic skeletons. , 2013, The Journal of organic chemistry.

[42]  Discovery of Potent Inhibitors of Schistosoma mansoni NAD⁺ Catabolizing Enzyme. , 2015, Journal of medicinal chemistry.

[43]  S. Batra.  Applications of Morita-Baylis-Hillman Reaction to the Synthesis of Natural Products and Drug Molecules , 2015 .

[44]  M. Sonoda,et al.  Proline-Mediated Transition Metal-Free Access to 1H-Indazolones from 2-Halobenzohydrazides. , 2016, The Journal of organic chemistry.

[45]  Zi-Ning Cui,et al.  Synthesis and Larvicidal Activity of Novel Thenoylhydrazide Derivatives , 2016, Scientific Reports.

[46]  H. Pellissier.  Recent developments in the asymmetric organocatalytic Morita−Baylis−Hillman reaction , 2017 .

[47]  Ralph C. Gomes,et al.  Intermolecular Stetter Reactions on Morita‐Baylis‐Hillman Adducts: an Approach to Highly Functionalized 1,4‐Dicarbonyl Compounds , 2017 .

[48]  Jian Wu,et al.  Synthesis and insecticidal activity of diacylhydrazine derivatives containing a 3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole scaffold , 2017, Chemistry Central Journal.

[49]  Tingting Liu,et al.  Mechanisms and stereoselectivities of phosphine-catalyzed Rauhut-Currier reaction between N-phenylmaleimide and 2-benzoyl acrylate: A computational investigation , 2017 .

[50]  S. Bősze,et al.  Synthesis and biological evolution of hydrazones derived from 4-(trifluoromethyl)benzohydrazide. , 2017, Bioorganic & medicinal chemistry letters.

[51]  Junbiao Chang,et al.  Annulation Reactions of In-Situ-Generated N-(Het)aroyldiazenes with Isothiocyanates Leading to 2-Imino-1,3,4-oxadiazolines. , 2018, Organic letters.