Oxidant-free, three-component synthesis of 7-amino-6H-benzo[c]chromen-6-ones under green conditions

An oxidant-free three-component synthesis of biologically significant 7-amino-6H-benzo[c]chromen-6-ones was established involving a Sc(OTf)3 catalyzed three-component reaction between primary amines, β-ketoesters and 2-hydroxychalcones under green conditions. In this strategy, both the B and C rings of 6H-benzo[c]chromen-6-ones were constructed simultaneously starting from acyclic precursors by generating four new bonds including two C–C, one C–N and one C–O in a single synthetic operation. The mechanism of this sequential cascade process involves the initial formation of a β-enaminone intermediate followed by Michael addition with 2-hydroxychalcone, intramolecular cyclization, dehydration, lactonization and aromatization steps. Unlike the related literature approaches, this reaction delivered the products without the addition of any external oxidants to achieve the key aromatization step.

[1]  J. Menéndez,et al.  Three-Component Synthesis of a Library of m-Terphenyl Derivatives with Embedded β-Aminoester Moieties. , 2018, ACS combinatorial science.

[2]  B. Bhanage,et al.  Electrodimerization of N‐Alkoxyamides for Zinc(II) Catalyzed Phenolic Ester Synthesis under Mild Reaction Conditions , 2018 .

[3]  Jun Xu,et al.  Electrochemical C-O Bond Formation: Facile Access to Aromatic Lactones. , 2018, Chemistry.

[4]  S. Luo,et al.  Organocatalytic Electrochemical C–H Lactonization of Aromatic Carboxylic Acids , 2018, Synthesis.

[5]  C. Cho,et al.  Microwave-Assisted Cyclization under Mildly Basic Conditions: Synthesis of 6 H-Benzo[ c]chromen-6-ones and Their 7,8,9,10-Tetrahydro Analogues. , 2018, The Journal of organic chemistry.

[6]  A. Shao,et al.  External Oxidant-Free Dehydrogenative Lactonization of 2-Arylbenzoic Acids via Visible-Light Photocatalysis. , 2018, The Journal of organic chemistry.

[7]  F. Mo,et al.  Oxidant-Free C(sp2)-H Functionalization/C-O Bond Formation: A Kolbe Oxidative Cyclization Process. , 2018, The Journal of organic chemistry.

[8]  J. Metternich,et al.  Vitamin Catalysis: Direct, Photocatalytic Synthesis of Benzocoumarins via (-)-Riboflavin-Mediated Electron Transfer. , 2018, Organic letters.

[9]  Long Zhang,et al.  Visible-light promoted arene C–H/C–X lactonization via carboxylic radical aromatic substitution , 2018 .

[10]  Srinivasarao Yaragorla,et al.  Amine-Triggered Highly Facile Oxidative Benzannulation Reaction for the Synthesis of Anthranilates under Solvent-Free Calcium(II) Catalysis , 2017, ACS omega.

[11]  B. Bhanage,et al.  tert-Butyl Nitrite-Mediated Synthesis of N-Nitrosoamides, Carboxylic Acids, Benzocoumarins, and Isocoumarins from Amides. , 2017, The Journal of organic chemistry.

[12]  Jie Gu,et al.  Palladium-Catalyzed Direct Annulation of Benzoic Acids with Phenols to Synthesize Dibenzopyranones. , 2017, Organic letters.

[13]  Hongwei Jin,et al.  Synthesis of dibenzopyranones and pyrazolobenzopyranones through copper(0)/Selectfluor system-catalyzed double CH activation/oxygen insertion of 2-arylbenzaldehydes and 5-arylpyrazole-4-carbaldehydes , 2017 .

[14]  D. Weix,et al.  Ruthenium-Catalyzed C–H Arylation of Diverse Aryl Carboxylic Acids with Aryl and Heteroaryl Halides , 2016, Organic letters.

[15]  J. Menéndez,et al.  Three-Component Synthesis of Pyrrole-Related Nitrogen Heterocycles by a Hantzsch-Type Process: Comparison between Conventional and High-Speed Vibration Milling Conditions , 2016 .

[16]  M. Matsumura,et al.  Formation of Lactones by Decarboxylation of Aromatic Diacids via TiO2-Mediated Photocatalytic Reactions in Acetonitrile Solution , 2016 .

[17]  Tingshun Zhu,et al.  Green and Rapid Access to Benzocoumarins via Direct Benzene Construction through Base‐Mediated Formal [4+2] Reaction and Air Oxidation , 2016 .

[18]  S. Mandal,et al.  Synthesis of DNA‐Intercalating 6H‐Benzo[c]chromen‐6‐one Derivatives through a Strategic Combination of Garratt–Braverman and Minisci Acyloxylation Reactions , 2016 .

[19]  M. Garazd,et al.  Natural Dibenzo[b,d]Pyran-6-Ones: Structural Diversity and Biological Activity , 2016, Chemistry of Natural Compounds.

[20]  Ofentse Mazimba.  Synthetic protocols on 6$H$-benzo[$c$]chromen-6-ones: a review , 2016 .

[21]  J. Menéndez,et al.  Expedient, catalyst-free, three-component synthesis of fused tetrahydropyridines in water , 2015 .

[22]  Vellaisamy Sridharan,et al.  Highly efficient regioselective synthesis of pyrroles via a tandem enamine formation–Michael addition–cyclization sequence under catalyst- and solvent-free conditions , 2015 .

[23]  N. Yamamoto,et al.  Scalable Synthesis of 8-Amino-3-hydroxy-6H-benzo[c]chromen-6-one: Key Intermediate for SEGRA via the Hurtley Reaction , 2015 .

[24]  Xuesen Fan,et al.  Synthesis of Aminonaphthopyranones and Aminonaphthochromenones by Blaise‐Reaction‐Initiated Cascade Procedures , 2014 .

[25]  J. Menéndez,et al.  Fully diastereoselective synthesis of polysubstituted, functionalized piperidines and decahydroquinolines based on multicomponent reactions catalyzed by cerium(IV) ammonium nitrate. , 2014, Chemistry.

[26]  I. Masesane,et al.  Reaction of ethyl acetoacetate and 2'-hydroxychalcones: Efficient route to 9-aryl-6H-benzo[c]chromen-6-ones , 2014 .

[27]  J. Menéndez,et al.  New 5-unsubstituted dihydropyridines with improved CaV1.3 selectivity as potential neuroprotective agents against ischemic injury. , 2014, Journal of medicinal chemistry.

[28]  Jin-Ming Gao,et al.  Secondary metabolites from the endophytic Botryosphaeria dothidea of Melia azedarach and their antifungal, antibacterial, antioxidant, and cytotoxic activities. , 2014, Journal of agricultural and food chemistry.

[29]  D. Lai,et al.  Natural Dibenzo-α-Pyrones and Their Bioactivities , 2014, Molecules.

[30]  Xiaoyi Wei,et al.  Chemical Constituents of the Endophytic FungusPhomopsissp. A240 Isolated fromTaxus chinensisvar.mairei , 2014 .

[31]  Y. R. Lee,et al.  An advanced and novel one-pot synthetic method for diverse benzo[c]chromen-6-ones by transition-metal free mild base-promoted domino reactions of substituted 2-hydroxychalcones with β-ketoesters and its application to polysubstituted terphenyls. , 2014, Organic & biomolecular chemistry.

[32]  Hongwei Liu,et al.  Chemical constituents from the rice fermented with the edible mushroom Pleurotus eryngii and their quinone oxidoreductase 1 inducing effect. , 2013, Fitoterapia.

[33]  Zhangjie Shi,et al.  Synthesis of dibenzopyranones through palladium-catalyzed directed C-H activation/carbonylation of 2-arylphenols. , 2013, Angewandte Chemie.

[34]  J. Menéndez,et al.  A β-enaminone-initiated multicomponent domino reaction for the synthesis of indoloquinolizines and benzoquinolizines from acyclic precursors. , 2013, Chemistry.

[35]  J. Menéndez,et al.  A new CAN-catalyzed domino process related to the Nenitzescu reaction: very concise access to fused ortho-indolequinones from simple precursors , 2013 .

[36]  Liang Xu,et al.  Benzopyranones from the Endophytic Fungus Hyalodendriella sp. Ponipodef12 and Their Bioactivities , 2012, Molecules.

[37]  Louise N. Dawe,et al.  Synthesis of 6H-dibenzo[b,d]pyran-6-ones using the inverse electron demand Diels-Alder reaction. , 2011, The Journal of organic chemistry.

[38]  T. Hosoya,et al.  PALMARIOLS A AND B, TWO NEW CHLORINATED DIBENZO-α-PYRONES FROM DISCOMYCETE LACHNUM PALMAE , 2010 .

[39]  J. Menéndez,et al.  Cerium(IV) ammonium nitrate as a catalyst in organic synthesis. , 2010, Chemical reviews.

[40]  J. Menéndez,et al.  Two-step stereocontrolled synthesis of densely functionalized cyclic beta-aminoesters containing four stereocenters, based on a new cerium(IV) ammonium nitrate catalyzed sequential three-component reaction. , 2008, Organic letters.

[41]  G. Schmeda-Hirschmann,et al.  Metabolites from Microsphaeropsis olivacea, an Endophytic Fungus of Pilgerodendron uviferum , 2005, Zeitschrift fur Naturforschung. C, Journal of biosciences.

[42]  T. Tanahashi,et al.  For Phenolics from the Cultured Lichen Mycobiont of Graphis scripta var. pulverulenta , 1997 .

[43]  D. Hart,et al.  Synthesis of defucogilvocarcin V isosteres via MAD-mediated conjugate addition of carbanions to naphthoquinone ketals , 1996 .

[44]  S. Danishefsky,et al.  A concise total synthesis of defucogilvocarcin V by application of the meyers biaryl strategy: ortho- and para-selective functionalizations of the A ring , 1988 .

[45]  J. Clardy,et al.  Antitumor agents from Streptomyces anandii: gilvocarcins V, M and E. , 1981, The Journal of antibiotics.

[46]  C. E. Stickings,et al.  Studies in the biochemistry of microorganisms. 90. Alternariol and alternariol monomethyl ether, metabolic products of Alternaria tenuis. , 1953, The Biochemical journal.