- Experiment and Theory of Bimetallic Pd-Catalyzed α-Arylation and Annulation for Naphthalene Synthesis
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We report the synthesis of bimetallic Pd(I) and Pd(II) complexes with bidentate 2-phosphinoimidazole ligands and their catalytic activity to generate substituted naphthalenes. This process involves the coupling of an aryl iodide and 2 equiv of a ketone via sequential ketone α-arylation and then annulation to generate disubstituted and tetrasubstituted naphthalenes in a regioselective manner. Excellent substrate scope for both aryl iodide and ketone partners is demonstrated, including that for heteroaryl iodides. Bimetallic Pd complexes are much more reactive than monometallic Pd catalysts in this transformation. Density functional theory calculations, isotope effect experiments, and substrate competition experiments were used to examine bimetallic mechanisms, reactivity, and selectivity.
- Ence, Chloe C.,Ess, Daniel H.,Gassaway, Kyle J.,Himes, Samuel R.,Larsen, Samantha G.,Martinez, Erin E.,Matu, Manase F.,Michaelis, David J.,Moreno, Mariur Rodriguez,Nazari, S. Hadi,Smith, Stacey J.,Valdivia-Berroeta, Gabriel A.
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p. 10394 - 10404
(2021/08/31)
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- Ruthenium-catalyzed coupling of α-carbonyl phosphoniums with sulfoxonium ylidesviaC-H activation/Wittig reaction sequences
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A Ru(ii)-catalyzed coupling of various α-carbonyl phosphoniums with sulfoxonium ylides has been realized for the facile synthesis of 1-naphthols in good to excellent yields. This oxidant-free transformation proceeds through Ru-catalyzed C-H activation of phosphoniums, Ru-carbene insertion, and intramolecular Wittig reaction processes.
- Chen, Tian,Ding, Zhiqiang,Guan, Yuqiu,Zhang, Ruike,Yao, Jinzhong,Chen, Zhangpei
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p. 2665 - 2668
(2021/03/16)
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- Ligand-Free and Solvent-Free Synthesis of 1,3-Disubstituted Naphthalenes through Stille Coupling
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A variety of 1,3-disubstituted naphthalenes have been prepared by palladium-catalyzed annulation of (o-ethynylphenyl)acetyl chloride with design of a new synthetic strategy by Stille coupling using functionalized organostannanes. The method affords excellent yields of the substituted naphthalenes and accommodates a wide variety of functional groups under mild conditions. Mechanistic studies show intramolecular cyclization as a major step following C-C bond coupling.
- Mkpenie, Victor,Rohand, Taoufik,Sbi, Sanae,Tanemura, Kiyoshi
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supporting information
p. 903 - 906
(2020/05/28)
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- Group 4 Diarylmetallocenes as Bespoke Aryne Precursors for Titanium-Catalyzed [2 + 2 + 2] Cycloaddition of Arynes and Alkynes
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Despite the ubiquity of reports describing titanium (Ti)-catalyzed [2 + 2 + 2] cyclotrimerization of alkynes, the incorporation of arynes into this potent manifold has never been reported. The in situ generation of arynes often requires fluoride, which instead will react with the highly fluorophilic Ti center, suppressing productive catalysis. Herein, we describe the use of group 4 diarylmetallocenes, CpR2MAr2 (CpR = C5H5, C5Me5; M = Ti, Zr), as aryne precursors for the Ti-catalyzed synthesis of substituted naphthalenes via coupling with 2 equiv of an alkyne. Fair-to-good yields of the desired naphthalene products could be obtained with 1% catalyst loadings, which is roughly an order of magnitude lower than similar reactions catalyzed by palladium or nickel. Additionally, naphthalenes find broad applications in the electronics, photovoltaics, and pharmaceutical industries, urging the discovery of more economic syntheses. These results indicate that aryne transfer from a CpR2M(?2-aryne) complex to another metal is a viable route for the introduction of aryne fragments into organometallic catalytic processes.
- Reiner, Benjamin R.,Tonks, Ian A.
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supporting information
p. 10508 - 10515
(2019/09/13)
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- Synthesis of Naphthalenyl Triflates via the Cationic Annulation of Benzodiynes with Triflic Acid
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A highly efficient and regioselective annulation of benzodiynes promoted by triflic acid has been developed. This protocol provides a step and atom-economic access to a series of naphthalenyl triflates. Furthermore, direct synthetic applications of this r
- Ge, Chenxin,Wang, Guohua,Wu, Panpan,Chen, Chao
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p. 5010 - 5014
(2019/07/08)
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- Substituent-Guided Palladium-Ene Reaction for the Synthesis of Carbazoles and Cyclopenta[ b]indoles
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An efficient palladium-catalyzed intramolecular Trost-Oppolzer type Alder-ene strategy was developed for the synthesis of carbazoles and cyclopenta[b]indoles from easily accessible(3-allyl-1H-indol-2-yl)methyl acetates. This strategy was extended for the synthesis of naphthalenes and dibenzobenzofurans as well. In addition, a short synthesis of antibacterial and antifungal natural product glycozoline and its analogues was also achieved.
- Yadav, Sonu,Hazra, Raju,Singh, Animesh,Ramasastry
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supporting information
(2019/05/07)
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- Substituent-Guided Palladium-Ene Reaction for the Synthesis of Carbazoles and Cyclopenta[b]indoles
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An efficient palladium-catalyzed intramolecular Trost-Oppolzer type Alder-ene strategy was developed for the synthesis of carbazoles and cyclopenta[b]indoles from easily accessible(3-allyl-1H-indol-2-yl)methyl acetates. This strategy was extended for the synthesis of naphthalenes and dibenzobenzofurans as well. In addition, a short synthesis of antibacterial and antifungal natural product glycozoline and its analogues was also achieved.
- Yadav, Sonu,Hazra, Raju,Singh, Animesh,Ramasastry
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supporting information
p. 2983 - 2987
(2019/05/10)
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- Palladium-Catalyzed Cascade Reaction of o-Bromobenzaldehydes with N-Sulfonylhydrazones: An Efficient Approach to the Naphthalene Skeleton
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A new strategy for the construction of the naphthalene backbone is described. The reaction essentially starts from two simple aldehydes. The key step is enabled by a palladium-carbene migratory insertion. After that, a sequence of reversible allylic alkylation and intramolecular condensation takes place to give the substituted naphthalene derivatives. Additional manipulations on the sulfonyl group in the product via palladium-catalyzed Kumada coupling were also investigated. (Figure presented.).
- Zhang, Heng,Yu, Yinghua,Huang, Shenlin,Huang, Xueliang
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p. 1576 - 1581
(2019/02/16)
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- Radical Addition/Cyclization Reaction of 2-Vinylanilines with Alkynes: Synthesis of Naphthalenes via Electron Catalysis
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A cascade radical addition/cyclization reaction of 2-vinylanilines with alkynes for the synthesis of biologically important naphthalene derivatives is reported. In this transformation, the in-situ-formed diazonium salts from 2-vinylanilines served as efficient aryl radical precursors and the reaction was run under metal-free conditions.
- Cao, Xia,Cai, Bao-Gui,Xu, Guo-Yong,Xuan, Jun
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supporting information
p. 3855 - 3858
(2018/11/27)
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- Synthesis of Polysubstituted Polycyclic Aromatic Hydrocarbons by Gold-Catalyzed Cyclization-Oxidation of Alkylidenecyclopropane-Containing 1,5-Enynes
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A gold-catalyzed tandem cyclization-oxidation of alkylidenecyclopropane-containing 1,5-enynes with 3,5-dibromo-pyridine N-oxide via a noncarbene model was developed, providing a range of synthetically valuable and useful arylacetaldehyde derivatives in mo
- Yu, Liu-Zhu,Wei, Yin,Shi, Min
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p. 4242 - 4247
(2017/07/24)
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- Ring-Opening/Expansion Rearrangement of Cycloprop[2,3]inden-1-ols Catalyzed by p-Toluenesulfonic Acid
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A divergent approach to generate either 1-hydroxymethylindenes (which could then be converted to benzofulvenes through a dehydration reaction) or naphthalenes by the rearrangement of cycloprop[2,3]inden-1-ols is reported. The effect of the cyclopropyl ring substitution pattern on ring-opening/expansion rearrangements of the substrates was systemically studied. (Figure presented.) .
- Li, Pei-Fang,Yi, Cheng-Bo,Ren, Shu-Jian,Qu, Jin
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supporting information
p. 2088 - 2092
(2016/07/16)
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- Gold versus palladium: A regioselective cycloisomerization of aromatic enynes
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Aromatic enynes can be transformed into arylnaphthalenes or benzofulvenes depending on the reaction conditions. Under gold(I) catalysis, exclusive or major 6-endo-dig cyclization took place leading to arylnaphthalenes. However, a catalytic system based on
- Aziz, Jessy,Frison, Gilles,Le Menez, Patrick,Brion, Jean-Daniel,Hamze, Abdallah,Alami, Mouad
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supporting information
p. 3425 - 3436
(2013/12/04)
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- Cyclization reaction for the synthesis of polysubstituted naphthalenes in the presence of Au(I) precatalysts
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Au(I)-catalyzed cyclization of alkenyl carbonyl compounds leading to a variety of substituted naphthalenes has been developed. This process exploits a dual function of the Au(I) catalyst: (1) the oxophilic nature of the Au(I) catalyst, counterintuitive to the π-acidic reactivities generally associated with Au catalysts, and (2) olefin isomerization supported by the outcome of isotope scrambling experiments. It cannot be completely excluded that TfOH is a true operative catalyst in this protocol. In view of the practicality, the unnecessity of isomerically pure starting material in this reaction is particularly attractive and valuable.
- Jagdale, Arun R.,Park, Jong Hyub,Youn, So Won
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experimental part
p. 7204 - 7215
(2011/10/17)
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- N-heterocyclic carbene-catalyzed (4 + 2) cycloaddition/decarboxylation of silyl dienol ethers with α,β-unsaturated acid fluorides
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Herein we report the first all-carbon N-heterocyclic carbene-catalyzed (4 + 2) cycloaddition. The reaction proceeds with α,β-unsaturated acid fluorides and silyl dienol ethers and produces 1,3-cyclohexadienes with complete diastereocontrol (dr >20:1) while demonstrating a new type of reaction cascade exploiting α,β-unsaturated acyl azoliums.
- Ryan, Sarah J.,Candish, Lisa,Lupton, David W.
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supporting information; experimental part
p. 4694 - 4697
(2011/05/28)
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- Gold-catalyzed annulation/fragmentation: Formation of free gold carbenes by retro-cyclopropanation
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The gold(I)-catalyzed cyclization of 1-(prop-2-yn-1-yl)-2-alkenylbenzenes substituted at the benzylic position with OR groups gives 1,3-disubstituted naphthalenes with concomitant fragmentation of the alkene. One of these annulations proceeds by a retro-cyclopropanation that leads to free gold(I) carbenes.
- Solorio-Alvarado, Cesar R.,Echavarren, Antonio M.
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supporting information; experimental part
p. 11881 - 11883
(2010/10/19)
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- FeCl3-catalyzed intramolecular hydroarylation of alkynes
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The intramolecular hydroarylation of alkynes using a substoichiometric amount of FeCl3 is described. When starting from tetrasubstituted substrates, products resulting from an unexpected toluene (or xylene) elimination are isolated in good yields.
- Dal Zotto, Christophe,Wehbe, Johny,Virieux, David,Campagne, Jean-Marc
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scheme or table
p. 2033 - 2035
(2009/04/07)
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- Bergman cyclization of sterically hindered substrates and observation of phenyl-shifted products
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Heating 1,2-bis(phenylethynyl)benzene in the presence of 1,4-cyclohexadiene at temperatures ranging from 260 to 360 °C yielded the expected Bergman product, 2,3-diphenylnaphthalene, as only a minor product (3 radicals. However, these transformations are relevant in solution chemistry as well as in more extreme environments such as those encountered during combustion, pyrolysis, and electric discharge heating. Copyright
- Lewis, Kevin D.,Matzger, Adam J.
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p. 9968 - 9969
(2007/10/03)
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- Synthesis of fused polycycles by 1,4-palladium migration chemistry
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Novel palladium migration/arylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution.
- Huang, Qinhua,Campo, Marino A.,Yao, Tuanli,Tian, Qingping,Larock, Richard C.
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p. 8251 - 8257
(2007/10/03)
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- A new titanium tetrachloride mediated annulation of α -aryl-substituted carbonyl compounds with alkynes: A simple and highly efficient method for the regioselective synthesis of polysubstituted naphthalene derivatives
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A new straightforward procedure has been developed for the synthesis of polysubstituted naphthalene derivatives. The reaction of α -aryl-substituted carbonyl compounds with terminal or internal alkynes in the presence of TiCl4 regioselectively generates substituted naphthalene derivatives in good to excellent yields.
- Kabalka, George W.,Ju, Yuhong,Wu, Zhongzhi
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p. 7915 - 7917
(2007/10/03)
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- REACTION OF PHENOLS AND THEIR DERIVATIVES WITH AROMATIC COMPOUNDS IN THE PRESENCE OF ACIDIC AGENTS. XIII. REACTION OF DERIVATIVES OF 2-NAPHTHOL WITH BENZENE. REGIOSELECTIVITY AND REACTION MECHANISM
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1-Methyl and 1-phenyl-2-naphthols react with benzene in the presence of aluminum chloride with the formation of 1-methyl-4-phenyl- and 1,4-diphenyl-2-tetralones respectively. 1,3-Naphthalenediol and its dimethyl ether enter into an analogous reaction in the presence of aluminum chloride or in the HF-SbF5 system with the formation of 3-phenyl-1-naphthol and its methyl ether respectively.It was concluded that the regioselectivity and other features of the condensations are due to the reactivity of the key intermediates of the reaction, i.e., the diprotonated forms of the 2-naphthols (dications) or, for the analogs in the presence of aluminum halides, the mono-C-protonated complexes of the tautomeric keto forms of naphthols with the aluminum halides.The latter agrees with the results from MNDO quantum-chemical calculations for the dications.
- Koltunov, K. Yu.,Repinskaya, I. B.,Shakirov, M. M.,Shchegoleva, L. N.
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- Tandem conjugate addition-aldol reaction to α,β-unsaturated esters and ketones using titanium amide
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Titanium dialkylamide, readily available, adds to a α,β-unsaturated esters and ketones in a conjugate addition mode to give ester and ketone enolates, respectively, which are successively quenched with electrophiles such as aldehydes and acetals. The aldol products can be readily converted to the corresponding deaminated or dehydrated derivatives selectively.
- Hosomi, Akira,Yanagi, Toshiharu,Hojo, Makoto
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p. 2371 - 2374
(2007/10/02)
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