Domino Radical Addition/Oxidation Sequence with Photocatalysis: One-Pot Synthesis of Polysubstituted Furans from α-Chloro-Alkyl Ketones and Styrenes.

A new domino reaction has been developed that allows the combination of styrenes and α-alkyl ketone radicals to afford a wide array of polysubstituted furans in good to excellent yields under mild and simple reaction conditions. The key to success of this novel protocol is the use of photocatalyst fac-Ir(ppy)3 and oxidant K2 S2 O8 . Mechanistic studies by a radical scavenger and photoluminescence quenching suggest that a radical addition/oxidation pathway is operable.

[1]  Qiang Liu,et al.  Preparation of 6-difluoromethylphosphonated phenanthridines by visible-light-driven radical cyclization of 2-isocyanobiphenyls , 2015 .

[2]  A. Antonchick,et al.  Copper(I)-Catalyzed Radical Addition of Acetophenones to Alkynes in Furan Synthesis. , 2015, Organic letters.

[3]  M. Wada,et al.  A Copper-Catalyzed Formal [3 + 2]-Cycloaddition for the Synthesis of All Different Aryl-Substituted Furans and Thiophenes. , 2015, The Journal of organic chemistry.

[4]  Jian-rong Gao,et al.  Indolizine Synthesis via Oxidative Cross-Coupling/Cyclization of Alkenes and 2-(Pyridin-2-yl)acetate Derivatives. , 2015, Organic letters.

[5]  Y. Lan,et al.  Tuning radical reactivity using iodine in oxidative C(sp(3))-H/C(sp)-H cross-coupling: an easy way toward the synthesis of furans and indolizines. , 2015, Chemical communications.

[6]  A. Hajra,et al.  Regioselective Synthesis of Multisubstituted Furans via Copper-Mediated Coupling between Ketones and β-Nitrostyrenes. , 2015, The Journal of organic chemistry.

[7]  A. Hajra,et al.  Copper-catalyzed regioselective synthesis of furan via tandem cycloaddition of ketone with an unsaturated carboxylic acid under air. , 2015, Organic & biomolecular chemistry.

[8]  Li‐Zhu Wu,et al.  Direct C-H difluoromethylenephosphonation of arenes and heteroarenes with bromodifluoromethyl phosphonate via visible-light photocatalysis. , 2014, Chemical communications.

[9]  D. Maiti,et al.  Radical based strategy toward the synthesis of 2,3-dihydrofurans from aryl ketones and aromatic olefins. , 2014, Organic letters.

[10]  M. Murata,et al.  Discovery of furan-2-carbohydrazides as orally active glucagon receptor antagonists. , 2014, Bioorganic & medicinal chemistry letters.

[11]  A. Studer,et al.  6-Perfluoroalkylated phenanthridines via radical perfluoroalkylation of isonitriles. , 2014, Organic letters.

[12]  W. Xiao,et al.  Visible-light-induced photocatalytic formyloxylation reactions of 3-bromooxindoles with water and DMF: the scope and mechanism , 2014 .

[13]  Shouyun Yu,et al.  Visible-light-mediated fluoroalkylation of isocyanides with ethyl bromofluoroacetates: unified synthesis of mono- and difluoromethylated phenanthridine derivatives. , 2014, Organic letters.

[14]  Rui Ge,et al.  Oxidative cross-coupling of allenyl ketones and organoboronic acids: expeditious synthesis of highly substituted furans. , 2014, Angewandte Chemie.

[15]  C. B. Mishra,et al.  8-(Furan-2-yl)-3-phenethylthiazolo[5,4-e][1,2,4]triazolo[1,5-c]pyrimidine-2(3H)-thione as novel, selective and potent adenosine A2A receptor antagonist , 2014, Neuroscience Letters.

[16]  Shouyun Yu,et al.  Synthesis of 6-alkylated phenanthridine derivatives using photoredox neutral somophilic isocyanide insertion. , 2013, Angewandte Chemie.

[17]  Li‐Zhu Wu,et al.  A novel intermolecular synthesis of γ-lactones via visible-light photoredox catalysis. , 2013, Organic letters.

[18]  Shouyun Yu,et al.  De novo synthesis of polysubstituted naphthols and furans using photoredox neutral coupling of alkynes with 2-bromo-1,3-dicarbonyl compounds. , 2013, Organic letters.

[19]  D. MacMillan,et al.  Visible light photoredox catalysis with transition metal complexes: applications in organic synthesis. , 2013, Chemical reviews.

[20]  Yuhong Zhang,et al.  Synthesis of polysubstituted furans via copper-mediated annulation of alkyl ketones with α,β-unsaturated carboxylic acids. , 2013, Organic letters.

[21]  L. Wojtas,et al.  Regioselective synthesis of multisubstituted furans via metalloradical cyclization of alkynes with α-diazocarbonyls: construction of functionalized α-oligofurans. , 2012, Journal of the American Chemical Society.

[22]  N. Chatani,et al.  Modular synthesis of phenanthridine derivatives by oxidative cyclization of 2-isocyanobiphenyls with organoboron reagents. , 2012, Angewandte Chemie.

[23]  P. Pérez,et al.  Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications , 2011 .

[24]  Jennifer J. Becker,et al.  Investigating the rate of photoreductive glucosyl radical generation. , 2011, Organic letters.

[25]  Corey R J Stephenson,et al.  Intermolecular atom transfer radical addition to olefins mediated by oxidative quenching of photoredox catalysts. , 2011, Journal of the American Chemical Society.

[26]  Jianji Wang,et al.  Tandem reaction of 1,2-allenic ketone with α-halo ketone or α-halo ester in water: an efficient and sustainable synthesis of 1,3,4'-tricarbonyl compounds , 2011 .

[27]  Jennifer J. Becker,et al.  Intermolecular addition of glycosyl halides to alkenes mediated by visible light. , 2010, Angewandte Chemie.

[28]  D. MacMillan,et al.  Enantioselective α-benzylation of aldehydes via photoredox organocatalysis. , 2010, Journal of the American Chemical Society.

[29]  B. Casey,et al.  Solvent-dependent oxidative coupling of 1-aryl-1,3-dicarbonyls and styrene. , 2009, Tetrahedron.

[30]  Mark E. Scott,et al.  Enantioselective alpha-trifluoromethylation of aldehydes via photoredox organocatalysis. , 2009, Journal of the American Chemical Society.

[31]  Joseph W Tucker,et al.  Electron-transfer photoredox catalysis: development of a tin-free reductive dehalogenation reaction. , 2009, Journal of the American Chemical Society.

[32]  David A. Nicewicz,et al.  Merging Photoredox Catalysis with Organocatalysis: The Direct Asymmetric Alkylation of Aldehydes , 2008, Science.

[33]  P. Langer,et al.  Synthesis of 2-Alkenyl-3-(alkoxycarbonyl)furans Based on Feist−Benary Cyclocondensation of (2,4-Dioxobutylidene)phosphoranes with α-Haloketones and α-Chloracetaldehyde , 2006 .

[34]  C. Willis,et al.  Diels-Alder chemistry at furan ring functionalized solid surfaces. , 2005, Chemical communications.

[35]  S. Xie,et al.  Metalloform-selective inhibitors of escherichia coli methionine aminopeptidase and X-ray structure of a Mn(II)-form enzyme complexed with an inhibitor. , 2004, Journal of the American Chemical Society.

[36]  R. Larock,et al.  AuCl(3)-catalyzed synthesis of highly substituted furans from 2-(1-alkynyl)-2-alken-1-ones. , 2004, Journal of the American Chemical Society.

[37]  Junliang Zhang,et al.  Catalytic regioselectivity control in ring-opening cycloisomerization of methylene- or alkylidenecyclopropyl ketones. , 2004, Journal of the American Chemical Society.

[38]  B. Katzenellenbogen,et al.  Synthesis and biological evaluation of a novel series of furans: Ligands selective for estrogen receptor α , 2001 .

[39]  D. Bebbington,et al.  Tributyltin hydride-mediated radical cyclisation of aldehydes and unsaturated ketones: the synthesis of hydroxy tetrahydrofurans, chromanols and related compounds , 2000 .

[40]  Chin‐Fa Lee,et al.  One-Pot Synthesis of Substituted Furans and Pyrroles from Propargylic Dithioacetals. New Annulation Route to Highly Photoluminescent Oligoaryls , 2000 .

[41]  R. Braslau,et al.  Synthesis of N-hydroxy peptides: chemical ligation of O-acyl hydroxamic acids. , 2000, Organic letters.

[42]  M. J. Medeiros,et al.  Electroreductive cyclisation of unsaturated halides catalysed by nickel macrocyclic complexes , 1999 .

[43]  H. Shinokubo,et al.  RADICAL ADDITION OF 2-IODOALKANAMIDE OR 2-IODOALKANOIC ACID TO ALKENOLS USING A WATER-SOLUBLE RADICAL INITIATOR IN WATER. A FACILE SYNTHESIS OF GAMMA -LACTONES , 1999 .

[44]  J. Bravo,et al.  Clay-catalyzed solventless addition reactions of furan with α,β-unsaturated carbonyl compounds☆ , 1998 .

[45]  Tomoaki Nakamura,et al.  Triethylborane-Mediated Atom Transfer Radical Cyclization Reaction in Water , 1998 .

[46]  D. Wayner,et al.  Redox Properties of Free Radicals , 1998 .

[47]  Sangyoub Lee,et al.  8-ENDO CYCLIZATION OF (ALKOXYCARBONYL)METHYL RADICALS : RADICAL WAYS FOR PREPARATION OF EIGHT-MEMBERED-RING LACTONES , 1998 .

[48]  Yuji Koga,et al.  Preparations of Furans from α-Bromo Ketones and Enol Ethers Catalyzed by a Rhenium(I) Nitrogen Complex , 1998 .

[49]  J. Bats,et al.  C-C-Bond Formation by the Palladium-Catalyzed Cycloisomerization/Dimerization of Terminal Allenyl Ketones: Selectivity and Mechanistic Aspects. , 1997, The Journal of organic chemistry.

[50]  H. Ohmori,et al.  Cyclopropanation by tandem radical [2 + 1] cycloaddition conducted by nickel complexes catalyzed electroreduction , 1997 .

[51]  V. Amarnath,et al.  Intermediates in the Paal-Knorr Synthesis of Furans , 1995 .

[52]  J. Iqbal,et al.  Transition Metal-Promoted Free-Radical Reactions in Organic Synthesis: The Formation of Carbon-Carbon Bonds , 1994 .

[53]  H. Ohmori,et al.  Indirect electroreductive radical cyclization of halogeno ethers using nickel(II) complexes as electron-transfer catalysts , 1992 .

[54]  J. A. Marshall,et al.  A mild method for the synthesis of furans. Application to 2,5-bridged furano macrocyclic compounds , 1990 .

[55]  N. Mahmoodi,et al.  Direct butyrolactone production using tin hydride , 1989 .

[56]  K. Mizuno,et al.  Regioselective double vicinal carbon-carbon bond forming reactions of electron-deficient alkenes by use of allylic stannanes and organoiodo compounds , 1988 .

[57]  D. Curran,et al.  Atom transfer cyclization reactions of α-iodo carbonyls , 1987 .

[58]  D. Tanner,et al.  Reduction of .alpha.-halo ketones by organotin hydrides. An electron-transfer-hydrogen atom abstraction mechanism , 1986 .

[59]  B. Lipshutz Five-membered heteroaromatic rings as intermediates in organic synthesis , 1986 .