- Ru(ii)-catalyzed allenylation and sequential annulation of: N -tosylbenzamides with propargyl alcohols
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We hereby report Ru(ii)-catalyzed C(sp2)-H allenylation of N-tosylbenzamides to access multi-substituted allenylamides. Furthermore, the allenylamides were converted to the corresponding isoquinolone derivatives via base mediated annulation. The current protocol features low catalyst loading, mild reaction conditions, high functional group compatibility and desired scalability. The unique functionality of the afforded allenes allowed further transformations to expand the practicality of the protocol. This journal is
- Kumar, Shreemoyee,Nair, Akshay M.,Volla, Chandra M. R.
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supporting information
p. 6280 - 6283
(2021/07/02)
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- Dual Palladium/Copper-Catalyzed anti-Selective Intermolecular Allenylsilylation of Terminal Alkynes: Entry to (E)-Silyl Enallenes
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A palladium-/copper-cocatalyzed three-component trans-allenylsilylation of terminal alkynes with propargyl acetates and PhMe2SiBpin is described, which is driven by the regioselective allenylation of the alkyne with propargyl acetates and then silylation. This method allows the simultaneous incorporation of an allene and silicon across the CC bond and provides a highly chemo-, regio-, and stereoselective alkyne difunctionalization route to the synthesis of valuable (E)-silyl enallenes. The utility of this method is highlighted by late-stage derivatization of bioactive compounds.
- Yang, Liang-Feng,Wang, Qiu-An,Li, Jin-Heng
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supporting information
p. 6553 - 6557
(2021/09/02)
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- Benzene-1,3,5-triyl Triformate (TFBen)-Promoted Palladium-Catalyzed Carbonylative Synthesis of 2-Oxo-2,5-dihydropyrroles from Propargyl Amines
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In this letter, we developed a palladium-catalyzed procedure for the cyclocarbonylation of propargyl amines. Benzene-1,3,5-triyl triformate (TFBen) has been explored as the CO source and also as the key promotor. Various substituted 2-oxo-dihydropyrroles were produced in a facile manner in good yields (up to 90%).
- Ying, Jun,Le, Zhengjie,Wu, Xiao-Feng
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supporting information
p. 194 - 198
(2020/01/03)
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- Metal-Free Regioselective Chloroazidation of Internal Alkynes
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A metal-free, room temperature protocol for the regioselective chloroazidation of internal alkynes is disclosed. The reactions of internal alkynes with trimethylsilyl azide (TMSN3) in the presence of 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) afforded the corresponding chloroazidoalkenes in good yields. This reaction has good functional group tolerance and is operationally simple.
- Huang, Bin,Liffert, Raphael,Linden, Anthony,Gademann, Karl
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supporting information
p. 981 - 984
(2019/01/04)
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- Synthesis of 4-Oxoisoxazoline N-Oxides via Pd-Catalyzed Cyclization of Propargylic Alcohols with tert-Butyl Nitrite
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A cyclization of propargylic alcohols with tert-butyl nitrite at room temperature in air was achieved using Pd(OAc)2 as catalyst. The first reported 4-oxoisoxazoline N-oxides could be directly accessed from a range of multisubstituted propargylic alcohols in moderate to excellent yields under mild conditions. Density functional theory calculations indicated that the reaction proceeds through a palladium-catalyzed NO2 addition that efficiently generates a ketoxime radical, which eventually produces 4-oxoisoxazoline N-oxide.
- Feng, Kai-Wen,Ban, Yong-Liang,Yuan, Pan-Feng,Lei, Wen-Long,Liu, Qiang,Fang, Ran
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supporting information
p. 3131 - 3135
(2019/05/10)
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- Flow rhodaelectro-catalyzed alkyne annulations by versatile C-H Activation: Mechanistic support for rhodium(III/IV)
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A flow-metallaelectro-catalyzed C-H activation was realized in terms of robust rhodaelectro-catalyzed alkyne annulations. To this end, a modular electro-flow cell with a porous graphite felt anode was designed to ensure efficient turnover. Thereby, a variety of C-H/N-H functionalizations proved amenable for alkyne annulations with high levels of regioselectivity and functional group tolerance, viable in both an inter- or intramolecular manner. The electro-flow C-H activation allowed easy scale up, while in-operando kinetic analysis was accomplished by online flow-NMR spectroscopy. Mechanistic studies suggest an oxidatively induced reductive elimination pathway on rhodium(III) in an electrocatalytic regime.
- Kong, Wei-Jun,Finger, Lars H.,Messinis, Antonis M.,Kuniyil, Rositha,Oliveira, Jo?o C.A.,Ackermann, Lutz
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supporting information
p. 17198 - 17206
(2019/10/28)
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- DBU-promoted carbonylative synthesis of 1,3-oxathiolan-2-ones from propargylic alcohols with TFBen as the CO source
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A DBU-promoted carbonylative cyclization of propargylic alcohols with sulfur was developed. Various 1,3-oxathiolan-2-ones were produced in 61-98% yields under mild conditions in the absence of metal catalysts. TFBen (benzene-1,3,5-triyl triformate) as an efficient and solid CO surrogate and S8 as an ideal sulfur source were employed and incorporated.
- Ying, Jun,Zhou, Chao,Wu, Xiao-Feng
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supporting information
p. 1065 - 1067
(2018/02/22)
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- Palladium(II)/N-Heterocyclic Carbene-Catalyzed Regioselective Heteroannulation of Tertiary Propargyl Alcohols and o-Haloanilines to form 2-Alkenylindoles
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Monometallic and bimetallic palladium(II)/N-heterocyclic carbene complexes appended with naphthalimide or bisnaphthalimide moieties were designed, synthesized, and characterized. Employment of these catalysts brings about the step-economic and regioselective heteroannulation of tertiary propargyl alcohols with o-haloanilines resulting in biologically and pharmaceutically relevant 2-alkenylindoles. Basis for the regioselective heteroannulation is unraveled by coordination of the propargylic hydroxy moiety to palladium during insertion. Embracing this methodology, a single regioisomer of unsymmetrical 2,3-disubstituted indoles could be achieved through late-stage modification. The role of the naphthalimide or bisnaphthalimide appended to the NHC on the catalytic efficiency has been studied. (Figure presented.).
- Panyam, Pradeep Kumar Reddy,Gandhi, Thirumanavelan
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supporting information
p. 1144 - 1151
(2017/04/13)
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- Highly Efficient Synthesis of Multi-Substituted Allenes from Propargyl Acetates and Organoaluminum Reagents Mediated by Palladium
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A simple and mild catalytic S N 2′ substitution reaction of propargyl acetates with organoaluminum reagents is reported. The S N 2′ substitution reaction of propargyl acetates with organoaluminum reagents mediated by Pd(PhP 3) 2 Cl 2 (1 mol%)/PPh 3 (2 mol%)/K 2 CO 3 in tetrahydrofuran at 60 °C for 3-4 hours afforded the corresponding multi-substituted allenes in good yields (up to 94%) with high selectivities (up to 99%). The process was simple and easily performed, which offers an efficient method to synthesize the multi-substituted allene derivatives.
- Zhang, Zhen,Shao, Xuebei,Zhang, Gang,Li, Qinghan,Li, Xinying
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p. 3643 - 3653
(2017/08/16)
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- Asymmetric Intermolecular Heck Reaction of Propargylic Acetates and Cycloalkenes to Access Fused Cyclobutenes
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An asymmetric Heck annulation of propargylic acetates with several types of cyclic olefins affords highly strained cyclobutenes in high enantioselectivity.
- Jiao, Zhiwei,Shi, Qi,Zhou, Jianrong Steve
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supporting information
p. 14567 - 14571
(2017/10/23)
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- Microwave-Assisted Organocatalyzed Rearrangement of Propargyl Vinyl Ethers to Salicylaldehyde Derivatives: An Experimental and Theoretical Study
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The microwave-assisted imidazole-catalyzed transformation of propargyl vinyl ethers (PVEs) into multisubstituted salicylaldehydes is described. The reaction is instrumentally simple, scalable, and tolerates a diverse degree of substitution at the propargylic position of the starting PVE. The generated salicylaldehyde motifs incorporate a broad range of topologies, spanning from simple aromatic monocycles to complex fused polycyclic systems. The reaction is highly regioselective and takes place under symmetry-breaking conditions. The preparative power of this reaction was demonstrated in the first total synthesis of morintrifolin B, a benzophenone metabolite isolated from the small tree Morinda citrifolia L. A DFT study of the reaction was performed with full agreement between calculated values and experimental results. The theoretically calculated values support a domino mechanism comprising a propargyl Claisen rearrangement, a [1,3]-H shift, a [1,7]-H shift (enolization), a 6π electrocyclization, and an aromatization reaction.
- Tejedor, David,Cotos, Leandro,Márquez-Arce, Daniel,Odriozola-Gimeno, Mikel,Torrent-Sucarrat, Miquel,Cossío, Fernando P.,García-Tellado, Fernando
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supporting information
p. 18280 - 18289
(2015/12/24)
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- Radical reactions of the cobalt-complexed propargyl acetals: Inter- and intramolecular variants
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Propargyl acetals are used as a new type of substrate in cobaltocene-induced radical reactions stereodirected by a π-bonded Co 2(CO)6 metal core. The experimental protocol involves treatment of the cobalt-complexed acetals with triflic anhydride, an in situ generation of ionic propargyl triflates, and a single-electron, low-temperature reduction of α-alkoxy-stabilized, Co2(CO)6-complexed propargyl cations. Inter- and intramolecular reactions provide a facile access to polyfunctional, topologically diverse 3,4-dialkoxy-1,5-alkadiynes and 3,4-dialkoxy-1,5-cyclodecadiynes with a predominant formation of the respective d,l-diastereomers (73-100% d,l). The stereo- and chemoselectivities are found to be dependent upon the (1) bulkiness of the gamma substituent (1,3-steric induction; d,l- 73-100%), (2) presence of a phosphorus ligand altering the π-bonded metal core (axial ligand induction; d,l- 91-97%), and (3) steric hindrance created by an alpha alkoxy group (1,1-steric induction; d,l- 83-92%).
- Melikyan, Gagik G.,Voorhees, Erin,Sepanian, Ruth
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- Multimetallic Ir-Sn3-catalyzed substitution reaction of π-activated alcohols with carbon and heteroatom nucleophiles
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An atom economic and catalytic substitution reaction of π-activated alcohols by a multimetallic IreSn3 complex has been demonstrated. The multimetallic IreSn3 complex can be easily synthesized from the reaction between [Cp*IrCl2]2 and SnCl2. In presence of as little as 1 mol % of the catalyst three different types of π-activated alcohols, namely benzyl, allyl, and propargyl alcohols, have been successfully transformed into alkylated products using carbon (arenes, heteroarenes, allyltrimethylsilane, and 1,3-dicarbonyls), nitrogen (sulfonamides), oxygen (alcohols), and sulfur (thiols) nucleophiles in very high yields. An electrophilic mechanism is proposed from the Hammett correlation study.
- Maity, Arnab Kumar,Chatterjee, Paresh Nath,Roy, Sujit
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p. 942 - 956
(2013/07/25)
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- Efficient solvent-free synthesis of tertiary propargylic alcohols from arylacetylenes and ketones promoted by tert-BuOK
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A mild and efficient method for the alkynylation of arylacetylenes with ketones promoted by tert-BuOK under solvent-free conditions was developed. The present green synthesis was applicable to many kinds of aromatic and aliphatic ketones providing good to excellent yields of tertiary propargylic alcohols. Graphical abstract: A mild and efficient method for the alkynylation of arylacetylenes with ketones promoted by tert-BuOK under solvent-free conditions was developed. The present green synthesis was applicable to many kinds of aromatic and aliphatic ketones providing good to excellent yields of tertiary propargylic alcohols.[Figure not available: see fulltext.]
- Chen, Shufeng,Yuan, Fang,Zhao, Haiying,Li, Baoguo
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p. 2391 - 2399
(2013/07/26)
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- Mild conversion of propargylic alcohols to α,β-unsaturated enones in ionic liquids (ILs); A new 'metal free' life for the Rupe rearrangement
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A mild and selective transition metal free protocol for the conversion of propargylic alcohols to cyclic and acyclic α,β-unsaturated enones via the Rupe rearrangement is reported. The method utilizes the Br?nsted acidic ionic liquid [BMIM-SO3H][OTf] as catalyst and [BMIM][PF 6] as solvent and offers the potential for recycling and reuse of the IL solvent. The feasibility to synthesize bicyclic fused cyclopentenone derivatives via a Rupe → Aldol → Nazarov sequence utilizing this protocol has also been demonstrated.
- Nandi, Ganesh C.,Rathman, Benjamin M.,Laali, Kenneth K.
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supporting information
p. 6258 - 6263
(2013/10/22)
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- Synthesis of 2,3-diiodoindenes and their applications in construction of 13H-indeno[1,2-l]phenanthrenes
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A series of 2,3-diiodoindene were synthesized at first, and 13H-indeno[1,2-l]phenanthrenes were then constructed via a Suzuki coupling reaction and subsequently a Scholl reaction. Structures of synthesized compounds were fully characterized by 1H NMR, 13C NMR, and HRMS. Their photophysical properties, such as UV-vis and FL spectra were investigated, and electronic properties were theoretically calculated by the software of Gaussian 03. The results suggested that these modified indene and indenophenanthrene compounds might have potential applications as light emitting materials.
- Zhou, Chao,Chen, Xiaopeng,Lu, Ping,Wang, Yanguang
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supporting information; experimental part
p. 2844 - 2850
(2012/05/05)
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- Hypoiodous acid initiated rearrangement of tertiary propargylic alcohols to α-iodoenones
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In the presence of an oxidant, sodium iodide is converted into hypoiodous acid which effects the rearrangement of tertiary propargylic alcohols to α-iodoenones in good yields.
- Moran, Wesley J.,Rodríguez, Arantxa
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supporting information
p. 8590 - 8592
(2013/01/15)
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- Mild and solvent-free alkynylation of ketones on the KF/alumina
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The solvent-free alkynylation of various ketones on the surface of KF/alumina under mild conditions is described. Copyright Taylor & Francis, Inc.
- Sharifi, Ali,Mirzaei, Mojtaba,Naimi-Jamal, M. Reza
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p. 1039 - 1044
(2007/10/03)
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- Organocatalytic alkynylation of aldehydes and ketones under phase-transfer catalytic conditions
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We developed alkynylations of various aldehydes and ketones under practical phase-transfer conditions at room temperature. The straightforward methodology combines one-pot synthesis and simple workup with good to excellent yields for propargylic alcohols derived from aliphatic aldehydes and ketones. Even aromatic aldehydes and ketones, could be transformed to the corresponding propargylic alcohols in somewhat lower yields. The yield depending on the amount of PT catalyst and NaOH concentration was also determined. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).
- Weil, Torsten,Schreiner, Peter R.
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p. 2213 - 2217
(2007/10/03)
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- Solvent-free addition of ethynylbenzene to ketones
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The addition of ethynylbenzene to ketones proceeded efficiently in the absence of a solvent to give tertiary alkynols in good yields.
- Miyamoto,Yasaka,Tanaka
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p. 185 - 186
(2007/10/03)
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- Perfume composition containing phenylethynyl carbinols
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The invention discloses perfume compositions containing one or more phenylethynyl carbinol compounds along with conventional perfume ingredients. The phenylethynyl carbinol compounds have the formula: STR1 wherein R1 and R2 is the same or different lower alkyl.
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