Iron-catalyzed trifluoromethylation of vinylcyclopropanes: facile synthesis of CF3–containing dihydronaphthalene derivatives

An efficient Fe(II)-catalyzed trifluoromethylation of vinylcyclopropanes was successfully developed. A series of CF3-containing dihydronaphthalene derivatives were prepared in moderate to high yields (up to 96%) under mild reaction conditions using the Togni reagent as the CF3 source.

[1]  Durga Prasad Hari,et al.  Cyclic Hypervalent Iodine Reagents for Atom-Transfer Reactions: Beyond Trifluoromethylation. , 2016, Angewandte Chemie.

[2]  R. Mason,et al.  Design, synthesis, and biological evaluation of water-soluble amino acid prodrug conjugates derived from combretastatin, dihydronaphthalene, and benzosuberene-based parent vascular disrupting agents. , 2016, Bioorganic & medicinal chemistry.

[3]  H. Neumann,et al.  Palladium-Catalyzed Trifluoromethylation of (Hetero)Arenes with CF3 Br. , 2016, Angewandte Chemie.

[4]  G. Haufe,et al.  Asymmetric Synthesis of Monofluorinated 1-Amino-1,2-dihydronaphthalene and 1,3-Amino Alcohol Derivatives. , 2016, Organic letters.

[5]  M. Shi,et al.  Iron- or Copper-Catalyzed Trifluoromethylation of Acrylamide-Tethered Alkylidenecyclopropanes: Facile Synthesis of CF3-Containing Polycyclic Benzazepine Derivatives , 2016 .

[6]  R. Melot,et al.  Palladium-Catalyzed C(sp(2))-H Alkylation of Aldehyde-Derived Hydrazones with Functionalized Difluoromethyl Bromides. , 2016, Angewandte Chemie.

[7]  R. Henry,et al.  Pd-Catalyzed Synthesis of Aryl and Heteroaryl Triflones from Reactions of Sodium Triflinate with Aryl (Heteroaryl) Triflates. , 2016, The Journal of organic chemistry.

[8]  R. Melot,et al.  C–H Difluoroalkylation of Aldehyde Hydrazones with Functionalized Difluoromethyl Bromides under Copper Catalysis , 2016 .

[9]  Jinbo Hu,et al.  Copper-Catalyzed Trifluoromethylation of Polysubstituted Alkenes Assisted by Decarboxylation. , 2016, Organic letters.

[10]  Xiangying Tang,et al.  Copper(I)-Catalyzed Intramolecular Trifluoromethylation of Methylenecyclopropanes. , 2015, Organic letters.

[11]  Jinxing Ye,et al.  Copper-Catalyzed Trifluoromethylazidation of Alkynes: Efficient Access to CF3-Substituted Azirines and Aziridines. , 2015, Angewandte Chemie.

[12]  Hao Xu,et al.  Asymmetric Annulation of Donor-Acceptor Cyclopropanes with Dienes. , 2015, Journal of the American Chemical Society.

[13]  B. Tan,et al.  Trifluoromethylation-initiated remote cross-coupling of carbonyl compounds to form carbon-heteroatom/carbon bonds. , 2015, Chemistry.

[14]  Lin Huang,et al.  Alkene Trifluoromethylation-Initiated Remote α-Azidation of Carbonyl Compounds toward Trifluoromethyl γ-Lactam and Spirobenzofuranone-Lactam , 2015 .

[15]  S. Schaus,et al.  Enantioselective synthesis of 1,2-dihydronaphthalene-1-carbaldehydes by addition of boronates to isochromene acetals catalyzed by tartaric acid. , 2015, Journal of the American Chemical Society.

[16]  P. Bonnet,et al.  Iron-catalyzed trifluoromethylation of enamide. , 2015, Chemistry.

[17]  F. Palacios,et al.  Carbon trifluoromethylation reactions of hydrocarbon derivatives and heteroarenes. , 2015, Chemical reviews.

[18]  Qun Liu,et al.  Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond. , 2015, Chemical reviews.

[19]  N. Shibata,et al.  Synthetic methods for compounds having CF3-S units on carbon by trifluoromethylation, trifluoromethylthiolation, triflylation, and related reactions. , 2015, Chemical reviews.

[20]  A. Togni,et al.  Electrophilic trifluoromethylation by use of hypervalent iodine reagents. , 2015, Chemical reviews.

[21]  Jinbo Hu,et al.  Good partnership between sulfur and fluorine: sulfur-based fluorination and fluoroalkylation reagents for organic synthesis. , 2015, Chemical reviews.

[22]  Zhange Feng,et al.  A general synthesis of fluoroalkylated alkenes by palladium-catalyzed Heck-type reaction of fluoroalkyl bromides. , 2015, Angewandte Chemie.

[23]  Jianwei Sun,et al.  Organocatalytic enantio- and diastereoselective synthesis of 1,2-dihydronaphthalenes from isobenzopyrylium ions. , 2015, Journal of the American Chemical Society.

[24]  Robert J. Phipps,et al.  Advances in Catalytic Enantioselective Fluorination, Mono-, Di-, and Trifluoromethylation, and Trifluoromethylthiolation Reactions , 2014, Chemical reviews.

[25]  Jin‐Hong Lin,et al.  Copper-catalyzed Tandem Trifluoromethylation/ Cyclization of Internal Alkynes , 2014 .

[26]  B. Tan,et al.  Enantioselective C-H bond functionalization triggered by radical trifluoromethylation of unactivated alkene. , 2014, Angewandte Chemie.

[27]  Zhaofeng Wang,et al.  Highly ortho‐Selective Trifluoromethylthiolation Reactions using a Ligand Exchange Strategy , 2014 .

[28]  Jun Xu,et al.  Copper-catalyzed endo-type trifluoromethylarylation of alkynes. , 2014, Chemical communications.

[29]  jin-quan yu,et al.  Exceedingly fast copper(II)-promoted ortho C-H trifluoromethylation of arenes using TMSCF₃. , 2014, Angewandte Chemie.

[30]  M. Sodeoka,et al.  Trifluoromethylation of alkenes with concomitant introduction of additional functional groups. , 2014, Angewandte Chemie.

[31]  Q. Ding,et al.  Copper-catalyzed direct trifluoromethylation of propiolates: construction of trifluoromethylated coumarins. , 2014, Organic letters.

[32]  Fei Wang,et al.  Copper-catalyzed intermolecular trifluoromethylarylation of alkenes: mutual activation of arylboronic acid and CF3+ reagent. , 2014, Journal of the American Chemical Society.

[33]  Johannes E. M. N. Klein,et al.  Fe-Catalyzed Nucleophilic Activation of C–Si versus Allylic C–O Bonds: Catalytic Trifluoromethylation of Carbonyl Groups versus Tandem Trifluormethylation–Allylation of Olefins , 2014 .

[34]  M. Sanford,et al.  Catalytic Cycle for Palladium-Catalyzed Decarbonylative Trifluoromethylation using Trifluoroacetic Esters as the CF3 Source , 2014 .

[35]  F. Qing,et al.  Oxidative trifluoromethylation and trifluoromethylthiolation reactions using (trifluoromethyl)trimethylsilane as a nucleophilic CF3 source. , 2014, Accounts of chemical research.

[36]  C. Valdés,et al.  A General Synthesis of α‐Trifluoromethylstyrenes through Palladium‐Catalyzed Cross‐Couplings with 1,1,1‐Trifluoroacetone Tosylhydrazone , 2014 .

[37]  Hong Liu,et al.  Fluorine in pharmaceutical industry: fluorine-containing drugs introduced to the market in the last decade (2001-2011). , 2014, Chemical reviews.

[38]  Fei Wang,et al.  Copper-catalyzed intermolecular trifluoromethylazidation of alkenes: convenient access to CF3 -containing alkyl azides. , 2014, Angewandte Chemie.

[39]  Yongping Liang,et al.  Copper-catalyzed trifluoromethylation of N-arylacrylamides "on water" at room temperature. , 2014, Chemical communications.

[40]  B. Tan,et al.  Efficient copper-catalyzed direct intramolecular aminotrifluoromethylation of unactivated alkenes with diverse nitrogen-based nucleophiles. , 2014, Chemistry.

[41]  B. Tan,et al.  Direct access to α-trifluoromethyl enones via efficient copper-catalyzed trifluoromethylation of Meyer-Schuster rearrangement. , 2014, Organic letters.

[42]  F. Qing,et al.  Copper-catalyzed three-component oxytrifluoromethylation of alkenes with sodium trifluoromethanesulfinate and hydroxamic acid. , 2013, Angewandte Chemie.

[43]  J. Li,et al.  Formation of dihydronaphthalenes via organocatalytic enatioselective Michael-aldol cascade reactions with arylalkanes. , 2013, Organic letters.

[44]  P. Zhou,et al.  Palladium-catalyzed insertion of α,β-unsaturated N-tosylhydrazones and trapping with carbon nucleophiles. , 2013, Chemical communications.

[45]  C. Nevado,et al.  Copper-catalyzed one-pot trifluoromethylation/aryl migration/desulfonylation and C(sp2)-N bond formation of conjugated tosyl amides. , 2013, Journal of the American Chemical Society.

[46]  Bin Yang,et al.  Copper-catalyzed tandem trifluoromethylation/semipinacol rearrangement of allylic alcohols. , 2013, Angewandte Chemie.

[47]  M. Sodeoka,et al.  Concise synthesis of oxindole derivatives bearing a 3-trifluoroethyl group: Copper-catalyzed trifluoromethylation of acryloanilides , 2013 .

[48]  M. Sodeoka,et al.  Iron-catalyzed trifluoromethylation with concomitant C-C bond formation via 1,2-migration of an aryl group. , 2013, Chemical communications.

[49]  Xiaowu Liu,et al.  Copper-catalyzed trifluoromethylation-initiated radical 1,2-aryl migration in α,α-diaryl allylic alcohols. , 2013, Angewandte Chemie.

[50]  S. Chemler,et al.  Copper-catalyzed oxidative Heck reactions between alkyltrifluoroborates and vinyl arenes. , 2013, Organic letters.

[51]  O. Baudoin,et al.  Copper-catalyzed trifluoromethylation of N,N-dialkylhydrazones. , 2013, Angewandte Chemie.

[52]  M. Sodeoka,et al.  Alkene trifluoromethylation coupled with C-C bond formation: construction of trifluoromethylated carbocycles and heterocycles. , 2013, Angewandte Chemie.

[53]  Le‐Ping Liu,et al.  Gold-catalyzed annulations of 2-alkynyl benzaldehydes with vinyl ethers: synthesis of dihydronaphthalene, isochromene, and bicyclo[2.2.2]octane derivatives. , 2013, Chemistry.

[54]  Zhangjie Shi,et al.  Palladium-catalyzed trifluoromethylation of aromatic C-H bond directed by an acetamino group. , 2013, Organic letters.

[55]  Q. Shen,et al.  Progress in Copper‐Mediated Formation of Trifluoromethylated Arenes , 2012 .

[56]  jin-quan yu,et al.  Pd(II)-catalyzed ortho trifluoromethylation of arenes and insights into the coordination mode of acidic amide directing groups. , 2012, Journal of the American Chemical Society.

[57]  S. Buchwald,et al.  Copper-Catalyzed Oxytrifluoromethylation of Unactivated Alkenes , 2012 .

[58]  L. Gade,et al.  Highly enantioselective copper-catalyzed electrophilic trifluoromethylation of β-ketoesters. , 2012, Journal of the American Chemical Society.

[59]  Jinbo Hu,et al.  Copper-catalyzed di- and trifluoromethylation of α,β-unsaturated carboxylic acids: a protocol for vinylic fluoroalkylations. , 2012, Angewandte Chemie.

[60]  F. Qing,et al.  Copper-catalyzed oxidative trifluoromethylation of terminal alkenes using nucleophilic CF3SiMe3: efficient C(sp3)-CF3 bond formation. , 2012, Organic letters.

[61]  S. Buchwald,et al.  Iron(II)-catalyzed trifluoromethylation of potassium vinyltrifluoroborates. , 2012, Angewandte Chemie.

[62]  Tao Wu,et al.  Palladium-catalyzed oxidative aryltrifluoromethylation of activated alkenes at room temperature. , 2012, Journal of the American Chemical Society.

[63]  F. Qing,et al.  Copper-catalyzed direct C-H oxidative trifluoromethylation of heteroarenes. , 2012, Journal of the American Chemical Society.

[64]  C. Bolm,et al.  Trace metal impurities in catalysis. , 2012, Chemical Society reviews.

[65]  W. Marsden.  I and J , 2012 .

[66]  S. Buchwald,et al.  The palladium-catalyzed trifluoromethylation of vinyl sulfonates. , 2011, Organic letters.

[67]  J. Wang,et al.  Copper-catalyzed C(sp3)-C(sp3) bond formation using a hypervalent iodine reagent: an efficient allylic trifluoromethylation. , 2011, Journal of the American Chemical Society.

[68]  Lei Liu,et al.  Copper-catalyzed trifluoromethylation of terminal alkenes through allylic C-H bond activation. , 2011, Journal of the American Chemical Society.

[69]  S. Buchwald,et al.  Copper-catalyzed trifluoromethylation of unactivated olefins. , 2011, Angewandte Chemie.

[70]  T. Ritter,et al.  Catalysis for fluorination and trifluoromethylation , 2011, Nature.

[71]  Guosheng Liu,et al.  Palladium-catalyzed oxidative trifluoromethylation of indoles at room temperature. , 2011, Chemistry.

[72]  M. Sanford,et al.  Mechanistic and computational studies of oxidatively-induced aryl-CF3 bond-formation at Pd: rational design of room temperature aryl trifluoromethylation. , 2011, Journal of the American Chemical Society.

[73]  V. Grushin,et al.  Aromatic trifluoromethylation with metal complexes. , 2011, Chemical reviews.

[74]  Andrew J. Neel,et al.  Dynamic kinetic asymmetric synthesis of substituted pyrrolidines from racemic cyclopropanes and aldimines: reaction development and mechanistic insights. , 2010, Journal of the American Chemical Society.

[75]  S. Buchwald,et al.  The Palladium-Catalyzed Trifluoromethylation of Aryl Chlorides , 2010, Science.

[76]  D. MacMillan,et al.  The productive merger of iodonium salts and organocatalysis: a non-photolytic approach to the enantioselective alpha-trifluoromethylation of aldehydes. , 2010, Journal of the American Chemical Society.

[77]  jin-quan yu,et al.  Pd(II)-catalyzed ortho-trifluoromethylation of arenes using TFA as a promoter. , 2010, Journal of the American Chemical Society.

[78]  P. G. Hultin,et al.  Pycnanthulignenes A-D, antimicrobial cyclolignene derivatives from the roots of Pycnanthus angolensis. , 2010, Journal of natural products.

[79]  S. Buchwald,et al.  On the role of metal contaminants in catalyses with FeCl3. , 2009, Angewandte Chemie.

[80]  A. Togni,et al.  Zinc-mediated formation of trifluoromethyl ethers from alcohols and hypervalent iodine trifluoromethylation reagents. , 2009, Angewandte Chemie.

[81]  Jun‐An Ma,et al.  Update 1 of: Asymmetric fluorination, trifluoromethylation, and perfluoroalkylation reactions. , 2008, Chemical reviews.

[82]  A. Togni,et al.  Reactivity of a 10-I-3 hypervalent iodine trifluoromethylation reagent with phenols. , 2008, The Journal of organic chemistry.

[83]  T. Yamakawa,et al.  Catalytic trifluoromethylation of uracil to 5-trifluoromethyluracil by use of CF3I and its industrial applications , 2008 .

[84]  P. Eisenberger,et al.  Mild electrophilic trifluoromethylation of secondary and primary aryl- and alkylphosphines using hypervalent iodine(iii)-CF(3) reagents. , 2008, Chemical communications.

[85]  K. Kirk.  Fluorination in Medicinal Chemistry: Methods, Strategies, and Recent Developments , 2008 .

[86]  S. Purser,et al.  Fluorine in medicinal chemistry. , 2008, Chemical Society reviews.

[87]  F. Diederich,et al.  Fluorine in Pharmaceuticals: Looking Beyond Intuition , 2007, Science.

[88]  M. Schlosser.  CF(3)-bearing aromatic and heterocyclic building blocks. , 2006, Angewandte Chemie.

[89]  P. Eisenberger,et al.  Novel 10-I-3 hypervalent iodine-based compounds for electrophilic trifluoromethylation. , 2006, Chemistry.

[90]  R. Hartmann,et al.  Synthesis and evaluation of heteroaryl-substituted dihydronaphthalenes and indenes: potent and selective inhibitors of aldosterone synthase (CYP11B2) for the treatment of congestive heart failure and myocardial fibrosis. , 2006, Journal of medicinal chemistry.

[91]  H. Davies,et al.  Highly diastereoselective and enantioselective C-H functionalization of 1,2-dihydronaphthalenes: a combined C-H activation/Cope rearrangement followed by a retro-Cope rearrangement. , 2004, Journal of the American Chemical Society.

[92]  F. Mollinedo,et al.  Synthesis and biological evaluation of new selective cytotoxic cyclolignans derived from podophyllotoxin. , 2004, Journal of medicinal chemistry.

[93]  M. Helliwell,et al.  Dearomatizing cyclization of arylsulfonylalkoxymethyl lithiums: a route to the podophyllotoxin skeleton. , 2003, Organic letters.

[94]  T. Kim,et al.  Synthesis of 1,3-disubstituted naphthalenes from the Baylis–Hillman acetates with the aid of manganese(III) acetate , 2002 .

[95]  Ernst Peter Kundig,et al.  Transition-metal-mediated dearomatization reactions. , 2000, Chemical reviews.

[96]  D. Grant,et al.  Carbon-13 magnetic resonance of hydroaromatics. 3. Conformation of 1,2,3,4-tetrahydrophenanthrene and 9,10-dihydrophenanthrene and their methyl derivatives , 1985 .