Catalytic Synthesis of 2H-Chromenes

2H-Chromenes (2H-1-benzopyran derivatives) display a broad spectrum of biological activities. The 2H-chromene substructure is an important structural motif present in a variety of medicines, natural products, and materials showing unique photophysical properties. Hence, the structural importance of the benzopyran moiety has elicited a great deal of interest in the field of organic synthesis and chemical biology to develop new and improved synthesis of these molecular skeletons. This review gives an up-to-date overview of different catalytic methodologies developed for the synthesis of 2H-chromenes and is structured around the three main approaches applied in catalytic 2H-chromene synthesis: (I) catalysis with (transition) metals, (II) metal-free Bronsted and Lewis acid/base catalysis, which includes examples of nonenantioselective organocatalysis, and (III) enantioselective organo-catalysis. The section in which the metal-catalyzed reactions are discussed describes different ring-closing strategies based ...

[1]  J. Mascareñas,et al.  Rhodium-catalyzed (5+1) annulations between 2-alkenylphenols and allenes: a practical entry to 2,2-disubstituted 2H-chromenes. , 2015, Angewandte Chemie.

[2]  M. Balcı,et al.  Intramolecular heterocyclization of O-propargylated aromatic hydroxyaldehydes as an expedient route to substituted chromenopyridines under metal-free conditions. , 2015, Organic letters.

[3]  Israel Fernández,et al.  Divergent reactivity of homologue ortho-allenylbenzaldehydes controlled by the tether length: chromone versus chromene formation. , 2015, Chemistry.

[4]  J. Wang,et al.  Palladium-catalyzed coupling of N-tosylhydrazones and β-bromostyrene derivatives: new approach to 2H-chromenes. , 2014, Organic & biomolecular chemistry.

[5]  S. Khodabakhshi,et al.  Synthesis of new 4-aroyl-pyrano[c]chromenes via a one-pot, three-component reaction based on aryl glyoxals , 2014 .

[6]  P. Liu,et al.  A copper(II) perchlorate-promoted tandem reaction of internal alkynol and salicyl N-tosylhydrazone: direct access to isochromeno[3,4-b]chromene. , 2014, Chemical communications.

[7]  T. Bhowmik,et al.  Substituted 3-E-styryl-2H-chromenes and 3-E-styryl-2H-thiochromenes: synthesis, photophysical studies, anticancer activity, and exploration to tricyclic benzopyran skeleton. , 2014, The Journal of organic chemistry.

[8]  S. Iborra,et al.  Bifunctional acid-base ionic liquid for the one-pot synthesis of fine chemicals: thioethers, 2H-chromenes and 2H-quinoline derivatives , 2014 .

[9]  Xinyi Yu,et al.  Catalytic enantioselective synthesis of 2-aryl-chromenes. , 2014, Chemical science.

[10]  Jie Wu,et al.  Access to 6H-naphtho[2,3-c]chromenes by a palladium-catalyzed reaction of 2-haloaryl allene with 2-alkynylphenol. , 2014, Chemical communications.

[11]  M. I. Ansari,et al.  Design and synthesis of ERα/ERβ selective coumarin and chromene derivatives as potential anti-breast cancer and anti-osteoporotic agents , 2014 .

[12]  X. Zhang,et al.  Metalloradical approach to 2H-chromenes. , 2014, Journal of the American Chemical Society.

[13]  B. Song,et al.  Novel 2H-chromen derivatives: design, synthesis and anticancer activity , 2014 .

[14]  Guoyu Yang,et al.  An Efficient Solvent-Free Synthesis of 2-Hydroxy-2-(trifluoromethyl)-2H-chromenes Using Silica-Immobilized L-Proline , 2013, Molecules.

[15]  N. Jain,et al.  Synthesis, anticancer activity and photophysical properties of novel substituted 2-oxo-2H-chromenylpyrazolecarboxylates. , 2013, European journal of medicinal chemistry.

[16]  Arindam Mukhopadhyay,et al.  Helicity as a steric force: stabilization and helicity-dependent reversion of colored o-quinonoid intermediates of helical chromenes. , 2013, Journal of the American Chemical Society.

[17]  Y. Murthy,et al.  Synthesis, structure activity relationship and mode of action of 3-substitutedphenyl-1-(2,2,8,8-tetramethyl-3,4,9,10-tetrahydro-2H,8H-pyrano[2,3-f]chromen-6-yl)-propenones as novel anticancer agents in human leukaemia HL-60 cells. , 2013, European journal of medicinal chemistry.

[18]  Jianzhang Zhao,et al.  Visible light-harvesting cyclometalated Ir(III) complexes with pyreno[4,5-d]imidazole C^N ligands as triplet photosensitizers for triplet–triplet annihilation upconversion , 2013 .

[19]  Ramin Miri,et al.  2H-chromene derivatives bearing thiazolidine-2,4-dione, rhodanine or hydantoin moieties as potential anticancer agents. , 2013, European journal of medicinal chemistry.

[20]  J. Snyder,et al.  Design and in vitro activities of N-alkyl-N-[(8-R-2,2-dimethyl-2H-chromen-6-yl)methyl]heteroarylsulfonamides, novel, small-molecule hypoxia inducible factor-1 pathway inhibitors and anticancer agents. , 2012, Journal of medicinal chemistry.

[21]  A. Kobayashi,et al.  Remarkable fluorescence enhancement of benzo[g]chromen-2-ones induced by hydrogen-bonding interactions with protic solvents , 2012, Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology.

[22]  Jianzhang Zhao,et al.  Visible-light harvesting iridium complexes as singlet oxygen sensitizers for photooxidation of 1,5-dihydroxynaphthalene. , 2012, Chemical communications.

[23]  B. Feringa,et al.  Catalytic asymmetric synthesis of chromenes and tetrahydroquinolines via sequential allylic alkylation and intramolecular Heck coupling. , 2012, Chemical communications.

[24]  A. Doyle,et al.  Nickel-catalyzed cross-coupling of chromene acetals and boronic acids. , 2012, Organic letters.

[25]  J. S. D. Melo,et al.  Synthesis of a Photochromic Fused 2H‐Chromene Capable of Generating a Single Coloured Species , 2012 .

[26]  Yizhou Dong,et al.  Antitumor agents. 289. Design, synthesis, and anti-breast cancer activity in vivo of 4-amino-2H-benzo[h]chromen-2-one and 4-amino-7,8,9,10-tetrahydro-2H-benzo[h]chromen-2-one analogues with improved water solubility. , 2012, Journal of natural products.

[27]  Nilanjana Majumdar,et al.  Simultaneous synthesis of both rings of chromenes via a benzannulation/o-quinone methide formation/electrocyclization cascade. , 2012, Journal of the American Chemical Society.

[28]  D. Hadjipavlou-Litina,et al.  Synthesis and biological evaluation of (2,5-dihydro-1H-pyrrol-1-yl)-2H-chromen-2-ones as free radical scavengers. , 2011, European journal of medicinal chemistry.

[29]  Jianxiong Jiang,et al.  Recyclable Tertiary Amine Modified Diarylprolinol Ether as Aminocatalyst for the Sequential Asymmetric Synthesis of Functionalized Cyclohexanes and Chromenes , 2011 .

[30]  T. Rosenau,et al.  Novel tocopherol derivatives. Part 32: On the bromination of pyrano[3,2-f]chromenes related to γ-tocopherol , 2011, Tetrahedron.

[31]  R. Hua,et al.  ReCl(CO)5-catalyzed cyclocondensation of phenols with 2-methyl-3-butyn-2-ol to afford 2,2-dimethyl-2H-chromenes , 2011 .

[32]  H. Miyabe,et al.  A multicomponent coupling reaction induced by insertion of arynes into the C=O bond of formamide. , 2011, Angewandte Chemie.

[33]  K. Lyssenko,et al.  A concise approach to chiral chromenes based on levoglucosenone , 2011 .

[34]  P. Schreiner,et al.  Enantioselective Synthesisof 2-Aryl-3-nitro-2H-chromenes Catalyzedby a Bifunctional Thiourea , 2011 .

[35]  J. Wang,et al.  Sequential Au(I)-catalyzed reaction of water with o-acetylenyl-substituted phenyldiazoacetates , 2011, Beilstein journal of organic chemistry.

[36]  Yan‐Chao Wu,et al.  Cascade reaction of β,γ-unsaturated α-ketoesters with phenols in trityl chloride/TFA system. Highly selective synthesis of 4-aryl-2H-chromenes and their applications. , 2011, Organic & biomolecular chemistry.

[37]  I. Lykakis,et al.  Ph3PAuNTf2 as a Superior Catalyst for the Selective Synthesis of 2H‐Chromenes: Application to the Concise Synthesis of Benzopyran Natural Products , 2011 .

[38]  U. Jana,et al.  Iron-catalyzed synthesis of functionalized 2H-chromenes via intramolecular alkyne-carbonyl metathesis. , 2011, Journal of Organic Chemistry.

[39]  M. Rueping,et al.  Chiral organic contact ion pairs in metal-free catalytic asymmetric allylic substitutions. , 2011, Journal of the American Chemical Society.

[40]  B. Sridhar,et al.  Facile Synthesis of Substituted Ethyl 2‐(Chloromethyl)‐2‐hydroxy‐2H‐1‐benzopyran‐3‐carboxylates , 2011 .

[41]  Ren‐Jie Song,et al.  Iron-mediated [3 + 2] or [3 + 3] annulation of 2-(2-(ethynyl)phenoxy)-1-arylethanones: selective synthesis of indeno[1,2-c]chromenes and 5H-naphtho[1,2-c]chromenes. , 2011, Organic letters.

[42]  C. S. Reddy,et al.  Synthesis and antimicrobial activity of novel 2‐(aryl)‐3‐[5‐(2‐oxo‐2H‐3‐chromenyl)‐1,3‐oxazol‐2‐yl]‐1,3‐thiazolan‐4‐ones , 2011 .

[43]  S. Schaus,et al.  Enantioselective addition of boronates to chromene acetals catalyzed by a chiral Brønsted acid/Lewis acid system. , 2010, Angewandte Chemie.

[44]  A. Aponick,et al.  A highly adaptable catalyst/substrate system for the synthesis of substituted chromenes. , 2010, Chemical communications.

[45]  P. Schneider,et al.  Enantioselective synthesis of iclaprim enantiomers--a versatile approach to 2-substituted chiral chromenes. , 2010, The Journal of organic chemistry.

[46]  N. S. S. Kumar,et al.  Photophysical investigation of 3-substituted 4-alkyl and/or 7-acetoxy coumarin derivatives--a study of the effect of substituents on fluorescence. , 2010, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[47]  Philip D. Campbell,et al.  Synthesis of function-oriented 2-phenyl-2H-chromene derivatives using L-pipecolinic acid and substituted guanidine organocatalysts. , 2010, Tetrahedron letters.

[48]  M. L. Patil,et al.  Enantioselective 6-endo-trig Wacker-type cyclization of 2-geranylphenols: application to a facile synthesis of (−)-cordiachromene , 2010 .

[49]  Jian-Wu Xie,et al.  Efficient kinetic resolution of racemic 3-nitro-2H-chromene derivatives catalyzed by Takemoto's organocatalyst. , 2010, Organic & biomolecular chemistry.

[50]  L. Liang,et al.  Iron‐Catalyzed Regioselective Hydroaryloxylation of CC Triple Bonds: An Efficient Synthesis of 2H‐1‐Benzopyran Derivatives , 2009 .

[51]  Alex C. Bissember,et al.  The Au(I)-catalyzed intramolecular hydroarylation of terminal alkynes under mild conditions: application to the synthesis of 2H-chromenes, coumarins, benzofurans, and dihydroquinolines. , 2009, The Journal of organic chemistry.

[52]  J. Yadav,et al.  Gallium(III) chloride-catalyzed three-component coupling of naphthol, alkyne and aldehyde: a novel synthesis of 1,3-disubstituted-3H-benzo[f] chromenes , 2009 .

[53]  Danqian Xu,et al.  Chiral amine/chiral acid as an excellent organocatalytic system for the enantioselective tandem oxa-Michael-aldol reaction. , 2009, Organic & biomolecular chemistry.

[54]  M. Adler,et al.  Direct, regioselective synthesis of 2,2-dimethyl-2H-chromenes. Total syntheses of octandrenolone and precocenes I and II , 2009 .

[55]  P. T. Perumal,et al.  Synthesis of Novel 3-Bromo-2H-chromene Derivatives: Palladium-Mediated IntramolecularCyclization of Aryl Propargyl Ethers , 2009 .

[56]  A. Bianucci,et al.  Predictive models, based on classification algorithms, for compounds potentially active as mitochondrial ATP-sensitive potassium channel openers. , 2009, Bioorganic & medicinal chemistry.

[57]  D. Uguen,et al.  Efficient Access to (All-rac)-α-Tocopherol Acetate by a Crombie Chromene Synthesis , 2009 .

[58]  A. J. Blake,et al.  Synthesis of (+/-)-likonide B (smenochromene D) using a regioselective Claisen rearrangement, separation of the enantiomers and stereochemical assignment. , 2009, Organic & biomolecular chemistry.

[59]  N. Petasis,et al.  Synthesis of 2H-chromenes and 1,2-dihydroquinolines from aryl aldehydes, amines, and alkenylboron compounds. , 2009, Journal of organometallic chemistry.

[60]  Benhur Godoi,et al.  Synthesis of organochalcogen propargyl aryl ethers and their application in the electrophilic cyclization reaction: an efficient preparation of 3-halo-4-chalcogen-2H-benzopyrans. , 2009, The Journal of organic chemistry.

[61]  C. R. Correia,et al.  The scope of the Heck arylation of enol ethers with arenediazonium salts: a new approach to the synthesis of flavonoids , 2009 .

[62]  R. I. Kureshy,et al.  SULFONIC ACID FUNCTIONALIZED MESOPOROUS SBA-15 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE SYNTHESIS OF CHROMENES FROM CHROMANOLS , 2009 .

[63]  Lizhi Zhao,et al.  A novel multicomponent reaction to synthesize substituted furo[3,2-c]chromenes via a Pd-catalyzed cascade process , 2008 .

[64]  S. Sankararaman,et al.  New pyrrolidine-triazole-based C2 symmetric organocatalysts and their utility in the asymmetric Michael reaction of β-nitrostyrenes and the synthesis of nitrochromenes , 2008 .

[65]  Zhen-yuan Xu,et al.  A Novel Enantioselective Catalytic Tandem Oxa‐Michael–Henry Reaction: One‐Pot Organocatalytic Asymmetric Synthesis of 3‐Nitro‐2H‐chromenes , 2008 .

[66]  D. Ramachary,et al.  A New One‐Pot Synthetic Approach to the Highly Functionalized (Z)‐2‐(Buta‐1,3‐dienyl)phenols and 2‐Methyl‐2H‐chromenes: Use of Amine, Ruthenium and Base‐Catalysis , 2008 .

[67]  M. Kodess,et al.  A simple and convenient synthesis of 4-methyl-3-nitro-2-trihalomethyl-2H-chromenes from N-unsubstituted imines of 2-hydroxyacetophenones and trichloro(trifluoro)ethylidene nitromethanes , 2008 .

[68]  Fei Liu,et al.  Synthesis of 2-substituted 2H-chromenes using potassium vinyltrifluoroborates. , 2008, Tetrahedron letters.

[69]  C. Moody,et al.  Synthesis of (±)-Smenochromene D (Likonide B) Using a Regioselective Claisen Rearrangement , 2008 .

[70]  Seung Bum Park,et al.  Diversity-oriented synthesis of privileged benzopyranyl heterocycles from s-cis-enones. , 2008, The Journal of organic chemistry.

[71]  F. C. D. Silva,et al.  One-Pot Synthesis of 2H-Chromene Derivatives from ortho-Naphthoquinones , 2007 .

[72]  K. Scheidt,et al.  Catalytic Enantioselective α‐Acylvinyl Anion Reactions of Silyloxyallenes , 2007 .

[73]  S. Delbaere,et al.  First synthesis of nitro-substituted 2,2-diphenyl-2H-1-benzopyrans via the ipso-nitration reaction , 2007 .

[74]  M. Shi,et al.  A facile synthetic route to 2 H-chromenes: reconsideration of the mechanism of the DBU-catalyzed reaction between salicylic aldehydes and ethyl 2-methylbuta-2,3-dienoate. , 2007, Chemistry.

[75]  P. S. Rao,et al.  Convenient One‐Pot Protocol for an Exclusive Synthesis of 4‐Cyano/ethoxycarbonyl‐2,2‐dimethyl‐2H‐chromene and/or 3‐Cyano/ethoxycarbonyl‐2‐isopropyl‐benzo[b]furan from a Single Oxo‐ylide , 2007 .

[76]  Jian Wang,et al.  One-pot approach to chiral chromenes via enantioselective organocatalytic domino oxa-Michael-aldol reaction. , 2007, Chemical communications.

[77]  R. Larock,et al.  Synthesis of 3,4-disubstituted 2H-benzopyrans through C-C bond formation via electrophilic cyclization. , 2007, The Journal of organic chemistry.

[78]  A. Córdova,et al.  Catalytic enantioselective domino oxa-michael/aldol condensations: asymmetric synthesis of benzopyran derivatives. , 2007, Chemistry.

[79]  Soizic Prado,et al.  A simple two steps ytterbium triflate‐catalysed preparation of 2,2‐dimethyl‐2h‐chromenes from salicylaldehydes and 2‐methylpropene , 2006 .

[80]  P. Laurent,et al.  Novel synthesis of 2-(trifluoromethyl)- and 2-(perfluoroalkyl)-2-hydroxy-2H-chromenes and their regiospecific reaction with silyl enol ethers. , 2006, The Journal of organic chemistry.

[81]  T. Govender,et al.  Organocatalytic synthesis of chiral benzopyrans , 2006 .

[82]  Yong Tang,et al.  Unexpected tandem ylide annulation reaction for controllable synthesis of 2H-chromenes and 4H-chromenes. , 2006, Organic letters.

[83]  V. Charushin,et al.  Reaction of polyhaloalkyl-substituted chromones, pyrones, and furanones with salicylaldehydes as a direct route to fused 2H-chromenes. , 2006, The Journal of organic chemistry.

[84]  M. Shi,et al.  Potassium Carbonate‐Catalyzed Reactions of Salicylic Aldehydes with Allenic Ketones and Esters: an Effective Way to Synthesize Functionalized 2H‐Chromenes , 2006 .

[85]  G. Fabrizi,et al.  4-aryl- and 4-vinyl-2,2-dialkyl-3-chromenes from tertiary 3-(o-bromophenyl)propynols via a palladium-catalyzed hydroarylation/ hydrovinylation-cyclization sequence , 2006 .

[86]  Lei Zhang,et al.  Polymer-supported palladacycles: efficient reagents for synthesis of benzopyrans with palladium recovery. Relationship among resin loading, Pd:P ratio, and reactivity of immobilized palladacycles. , 2006, The Journal of organic chemistry.

[87]  C. Nevado,et al.  Intramolecular hydroarylation of alkynes catalyzed by platinum or gold: mechanism and endo selectivity. , 2006, Chemistry.

[88]  D. Gibson,et al.  Synthesis and antitumor activity of quinonoid derivatives of cannabinoids. , 2004, Journal of medicinal chemistry.

[89]  B. Love,et al.  Coumarins in polymers: from light harvesting to photo-cross-linkable tissue scaffolds. , 2004, Chemical reviews.

[90]  R. Larock,et al.  Synthesis of Heterocycles via Palladium π-Olefin and π-Alkyne Chemistry , 2004 .

[91]  Douglas A. Horton,et al.  The combinatorial synthesis of bicyclic privileged structures or privileged substructures. , 2003, Chemical reviews.

[92]  K. Lee,et al.  Isolation of rhododaurichromanic acid B and the anti-HIV principles rhododaurichromanic acid A and rhododaurichromenic acid from Rhododendron dauricum , 2001 .

[93]  M. G. Hutchings,et al.  Chromic Phenomena: Technological Applications of Colour Chemistry , 2001 .

[94]  F. Rutjes,et al.  Synthesis of 2-substituted chromenes via ring-closing metathesis and stable 1-benzopyrylium ions , 2000 .

[95]  E. Skrzypczak‐Jankun,et al.  Why drinking green tea could prevent cancer , 1997, Nature.

[96]  A. Mizutani,et al.  Cesium Fluoride-mediated Claisen Rearrangements of Phenyl Propargyl Ethers: Substituent Effects of an ortho-Alkoxy Group on the Benzene Ring or Modified Propargyl Residues , 1997 .

[97]  W. Chai,et al.  Stereoselective syntheses of substituted pterocarpans with anti-HIV activity, and 5-aza-/5-thia-pterocarpan and 2-aryl-2,3-dihydrobenzofuran analogues. , 1996, Bioorganic & medicinal chemistry.

[98]  C. D. Gabbutt,et al.  Pyrans and their Benzo Derivatives - Synthesis , 1996 .

[99]  F. Pérez-Flores,et al.  Bentonitic earth catalyzed rearrangement of aryl 1,1‐dimethylpropargyl ethers. Synthesis of 2,2‐dimethyl‐2H‐1‐benzopyrans , 1995 .

[100]  J. M. Rao,et al.  Synthesis of Benzofurans Via Tandem Intramolecular Wittig and 3,3-Sigmatropic Reaction of Phenoxyacetyl-Cyanomethylenetriphenylphosphoranes , 1987 .

[101]  J. M. Rao,et al.  Tandem intramolecular wittig and claisen rearrangement reactions in the thermolysis of 2-methyl-2-phenoxy-propionyl-cyanomethylenetriphenylphosphoranes: synthesis of substituted 2H-1-benzopyrans and benzofurans , 1987 .

[102]  R. Yadla,et al.  Thermolysis of phenoxyacetyl-cyanomethylenetriphenylphosphoranes-tandem intramolecular Wittig and Claisen rearrangements reactions , 1987 .

[103]  K. Balasubramanian,et al.  Claisen rearrangement of aryl propargyl ethers in poly(ethylene glycol)- a remarkable substituent and solvent effect , 1983 .

[104]  A. Diplock The Chemistry of Heterocyclic Compounds: Chromenes, Chromanones and Chromones , 1978 .

[105]  M. Harfenist,et al.  Influence of structure on the rate of thermal rearrangement of aryl propargyl ethers to the chromenes. Gem-dimethyl effect , 1972 .