- Stereodivergent Palladium- And Rhodium-Catalyzed Intramolecular Addition of Tosylureas to Allenes: Diastereoselective Synthesis of Tetrahydropyrimidinones
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The intramolecular addition of tosylureas to allenes is highly syn-/anti-diastereoselective when employing a palladium or rhodium-based catalytic system and affords 1,3-cyclic ureas. Under palladium catalysis a range of thermodynamic anti-tetrahydropyrimi
- Breit, Bernhard,Geissler, Arne G. A.,Riesterer, Jasmin R.
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supporting information
p. 9168 - 9172
(2021/12/06)
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- Allylation and propargylation of aldehydes mediated byin situgenerated zinc from the redox couple of Al and ZnCl2in 2N HCl
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A simple one pot allylation and propargylation of aldehydes mediated by zinc(0), which isin situgenerated from the redox couple of Al and ZnCl2in 2N HCl, is demonstrated to afford the corresponding homoallyl and homopropargyl alcohols with exce
- Mondal, Bibhas,Adhikari, Utpal,Hajra, Partha Pratim,Roy, Ujjal Kanti
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p. 7163 - 7173
(2021/05/03)
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- Synthesis of vinylic sulfones in aqueous media
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A green method for the sulfination of allenic carbonyl compounds to access a wide variety of vinylic sulfones is developed. This reaction works in aqueous media under very mild conditions. This reaction is atom economic. A wide variety of vinylic sulfones could be obtained in moderate to excellent yields with wide functional group tolerance. The efficiency of this method is demonstrated in some reactions where the desired products can be isolated by filtration.
- Goh, Jeffrey,Maraswami, Manikantha,Loh, Teck-Peng
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supporting information
p. 1060 - 1065
(2021/02/16)
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- Formal metal-free γ-arylation of 1,3-dicarbonyl compounds: Via an isomerisation/1,4-addition/[3,3]-sigmatropic rearrangement sequence
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A metal-free redox arylation of alkynes with sulfoxides has been developed to provide unconventional access to diverse γ-arylated 1,3-dicarbonyl compounds in an atom-economical manner. Mechanistic studies suggest that a conjugated allenone intermediate was generated in situ, which solves the problem of reactivity and regioselectivity of unsymmetrical dialkyl-substituted internal alkynes and enables the functionalisation of a broad range of substrates bearing electron-withdrawing functional groups. The resulting arylated 1,3-dicarbonyl compounds are versatile and useful building blocks for further functionalisation. This journal is
- Guan, Xi-Dong,Lu, Shi-Chao,Wen, Fu-Qiang
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supporting information
p. 8964 - 8968
(2021/11/27)
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- One-pot, regioselective synthesis of homopropargyl alcohols using pro-pargyl bromide and carbonyl compound by the mg-mediated reaction under solvent-free conditions
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The elimination of volatile organic solvents in organic synthesis is the most important goal in “Green” chemistry. We report a simple, efficient and facile method for the addition of progargyl bromide to carbonyl compounds using Mg metal as a mediator under solvent-free conditions which could regioselectively generate homopropargyl alcohols efficiently in good to excellent yields. The procedure has advantages such as short reaction time, operationally simple, excellent product yields, high regioselectivity and organic solvent-free.
- Devaramani, Samrat,Li, Shunxi,Ma, Xiaofang,Xu, Daqian,Zhao, Guohu
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supporting information
p. 438 - 442
(2020/04/21)
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- Revisiting the Addition of in-situ Nucleophiles to Allenic Ketones: An Entry Towards Synthesis of Benzodioxins
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The manuscript delineates a revisit towards regioselective addition of in situ generated negative nucleophiles to allenic ketones in the presence of a base. A wide variety of allenic ketones as well as nucleophiles are viable in this transformation. A dir
- Sahoo, Sushree Ranjan,Sarkar, Debayan
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supporting information
p. 1727 - 1731
(2020/03/13)
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- Acyloxy Rearrangement-Triggered Regioselective Hydration of ?-Acetoxy-α,β-Alkynoates/Halo Alkynes
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Herein, we report a simple, efficient, highly regioselective, and broad-scope hydration method that is facilitated by an unusual interception of an electrophilic intermediate by water generated via acetate group participation during [3,3]-acyloxy rearrang
- Mendhekar, Kishor L.,Mohapatra, Debendra K.,Pradhan, Tapas R.
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p. 4881 - 4895
(2020/05/01)
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- Efficient method for propargylation of aldehydes promoted by allenylboron compounds under microwave irradiation
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The propargylation of aldehydes promoted by microwave irradiation using allenylboron compounds in a chemo- and regioselective way is described. The corresponding products were obtained in short reaction time, high yield and purity without the need of any solvent when allenylboronic acid pinacol ester was used, or using a minimal amount of acetone when potassium allenyltrifluoroborate was used.
- Andrade, Silvia R. C. P.,Freitas, Jucleiton J. R.,Freitas, Juliano C. R.,Freitas, Queila P. S. B.,Menezes, Paulo H.,Oliveira, Roberta A.
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supporting information
p. 168 - 174
(2020/03/27)
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- Synthesis, characterization of active Sn(0), and its application in selective propargylation of aldehyde at room temperature in water
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Active Sn(0) particles are synthesized in high yields by the chemical reduction of the blue-black stannous oxide using freshly prepared sodium stannite solution as reducing agent at 40 °C and 60 °C. The Sn(0) particles are characterized using powder XRD, SEM, and DSC. The as-synthesized Sn(0) particles are applied as reagent for the regioselective synthesis of homopropargyl alcohols from propargyl bromide and aldehydes in distilled water at room temperature (in 50%-84% yields). No assistance of heat, microwave, ultrasound, organic co-solvent, co-reagent, or inert atmosphere is required for this reaction. The propargylation reaction is highly chemoselective towards aldehyde over other less electrophilic carbonyl functional groups such as ketone, amide, and carboxylic acid. Our in-house synthesized homopropargyl alcohols can be used to synthesize conjugated 1,3-diynes.
- Chatterjee, Paresh Nath,Paul, Dipankar,Sawkmie, Micky Lanster,Sinha, Arun Kumar,Khatua, Snehadrinarayan
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supporting information
p. 29 - 36
(2019/01/10)
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- Synthesis and characterization of nano?zinc wire using a self designed unit galvanic cell in aqueous medium and its reactivity in propargylation of aldehydes
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Electrochemistry is used for propargylation of carbonyls in aqueous ZnCl2 medium. For electrochemical process we designed a unit galvanic cell. ZnCl2 is used as stoichiometric reagent and causes electrochemical deposition of zinc in
- Mondal, Bibhas,Mandal, Siba Prasad,Kundu, Mousumi,Adhikari,Roy, Ujjal Kanti
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supporting information
p. 4669 - 4675
(2019/07/22)
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- A facile lipase-catalyzed KR approach toward enantiomerically enriched homopropargyl alcohols
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Compounds possessing propargylic (prop-2-ynylic) system are very important building blocks for organic chemistry. Among them, preparation of enantiomeric homopropargyl alcohols (but-3-yn-1-ols) constitutes a key-challenge for asymmetric synthesis and thus
- Borowiecki, Pawe?,Dranka, Maciej
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supporting information
(2019/02/14)
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- A bicyclization reaction with two molecular allenyl ketones and isocyanides: Synthesis of a lactone-containing azaspirocycle derivative
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A novel bicyclization reaction of two molecular allenyl ketones and isocyanides has been disclosed. This strategy allows for the construction of structurally complex spirocyclic lactam-lactone systems in an efficient manner. This protocol also demonstrate
- Yuan, Hongdong,Tang, Chongrong,Su, Shikuan,Cui, Lei,Jia, Xueshun,Li, Chunju,Li, Jian
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supporting information
p. 7231 - 7234
(2019/07/02)
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- Fe-Catalyzed tandem cyclization for the synthesis of 3-nitrofurans from homopropargylic alcohols and Al(NO3)3·9H2O
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Al(NO3)3·9H2O as a nitro source for the synthesis of 3-nitrofurans from homopropargylic alcohols through Fe-catalyzed tandem cyclization is described. In this transformation, the substituted nitrofurans are obtained throug
- Wang, Ting,Jiang, Yong,Wang, Yanyan,Yan, Rulong
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supporting information
p. 5232 - 5235
(2018/08/03)
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- Electrophilic cyclization and intermolecular acetalation of 2-(4- hydroxybut-1-yn-1-yl)benzaldehydes: Synthesis of diiodinated diepoxydibenzo[c,k][1,9]dioxacyclohexadecines
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An expedient strategy for the preparation of diiodinated diepoxydibenzo[c,k][1,9]dioxacyclohexadecines from readily available 2-(4-hydroxybut-1-yn-1-yl)- benzaldehydes through electrophile-triggered tandem cyclization/ intermolecular acetalation sequence
- Wang, Jia,Zhu, Hai-Tao,Chen, Si,Luan, Cheng,Xia, Yu,Shen, Yi,Li, Ying-Xiu,Hua, Yingxi,Liang, Yong-Min
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p. 10641 - 10649
(2018/05/31)
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- C-Propargylation Overrides O-Propargylation in Reactions of Propargyl Chloride with Primary Alcohols: Rhodium-Catalyzed Transfer Hydrogenation
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The canonical SN2 behavior displayed by alcohols and activated alkyl halides in basic media (O-alkylation) is superseded by a pathway leading to carbinol C-alkylation under the conditions of rhodium-catalyzed transfer hydrogenation. Racemic and asymmetric propargylations are described.
- Liang, Tao,Woo, Sang Kook,Krische, Michael J.
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supporting information
p. 9207 - 9211
(2016/08/05)
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- Regioselective propargylation of aldehydes using potassium allenyltrifluoroborate promoted by tonsil
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The propargylation of aldehydes using potassium allenyltrifluoroborate promoted by tonsil, an inexpensive and readily available clay, in a chemo- and regioselective way is described. The method is simple and avoids the use of air and moisture sensitive organometallics and products were obtained in good to moderate yields.
- Freitas, Jucleiton J.R.,Couto, Tulio R.,Cavalcanti, Italo H.,Freitas, Juliano C.R.,Barbosa, Queila P.S.,Oliveira, Roberta A.
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supporting information
p. 760 - 765
(2016/02/05)
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- Propargylation of aldehydes using potassium allenyltrifluoroborate
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The commercially available resin Amberlyst A-31 was efficiently used to promote the propargylation of aldehydes using potassium allenyltrifluoroborate. The method is simple and fast, and the products were obtained in short reaction times in high yields and purity at room temperature in a regio- and chemoselective manner.
- Couto, Tlio R.,Freitas, Jucleiton J. R.,Freitas, Juliano C. R.,Cavalcanti, Italo H.,Menezes, Paulo H.,Oliveira, Roberta A.
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- A practical procedure of propargylation of aldehydes
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An operationally simple procedure of propargylation of aldehydes in moist solvent (distilled THF) has been developed through direct addition of propargyl bromide to aldehyde substrates mediated with low valent iron or tin. The metals were spontaneously pr
- Ghosh, Papiya,Chattopadhyay, Angshuman
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p. 5202 - 5205
(2012/11/06)
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- Gold-catalyzed oxidative rearrangement of homopropargylic ether via oxonium ylide
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Synthetically useful α,β-unsaturated carbonyl compounds were obtained from gold-catalyzed oxidative rearrangement of homopropargylic ether under mild reaction conditions. Gold carbenoid and oxonium ylide are proposed as key intermediates.
- Xu, Mei,Ren, Tian-Tian,Li, Chuan-Ying
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supporting information
p. 4902 - 4905,4
(2020/09/16)
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- Efficient synthesis of γ-lactones via gold-catalyzed tandem cycloisomerization/oxidation
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A novel Au-catalyzed tandem cycloisomerization/oxidation of homopropargyl alcohols was developed. Various γ-lactones can be accessed readily by utilizing this strategy. Notably, the mechanism of this reaction is distinctively different from the related Ru-catalyzed reactions where the ruthenium vinylidene intermediate was proposed.
- Shu, Chao,Liu, Meng-Qi,Sun, Yu-Zhe,Ye, Long-Wu
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supporting information
p. 4958 - 4961,4
(2012/12/12)
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- Efficient synthesis of γ-lactones via gold-catalyzed tandem cycloisomerization/oxidation
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A novel Au-catalyzed tandem cycloisomerization/oxidation of homopropargyl alcohols was developed. Various γ-lactones can be accessed readily by utilizing this strategy. Notably, the mechanism of this reaction is distinctively different from the related Ru-catalyzed reactions where the ruthenium vinylidene intermediate was proposed.
- Shu, Chao,Liu, Meng-Qi,Sun, Yu-Zhe,Ye, Long-Wu
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supporting information
p. 4958 - 4961
(2013/01/15)
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- A new synthesis of γ-butyrolactones via AuCl3- or Hg(II)-catalyzed intramolecular hydroalkoxylation of 4-bromo-3-yn-1-ols
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An efficient conversion of 4-bromo-3-yn-1-ols to γ-butyrolactones via AuCl3-catalyzed electrophilic cyclization (hydroxyl-assisted regioselective hydration) in wet toluene is described. Various secondary and tertiary alcohols including benzylic systems were found to be equally reactive with moderate to excellent yields obtained in all cases.
- Reddy, Maddi Sridhar,Kumar, Yalla Kiran,Thirupathi, Nuligonda
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scheme or table
p. 824 - 827
(2012/04/05)
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- A halide-initiated aza-Baylis-Hillman reaction: Generation of unnatural amino acids
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A series of allenic ketones react with a glyoxylate-derived imine in the presence of MgBr2 through an aza-Morita-Baylis-Hillman (MBH) reaction. The isolation of a variety of unnatural amino acids with unique allene-containing functional groups
- Davis, Lindsey O.,Tobey, Suzanne L.
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supporting information; experimental part
p. 6078 - 6081
(2011/01/04)
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- One-pot, solvent-free regioselective addition reactions of propargyl bromide to carbonyl compounds mediated by Zn-Cu couple
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A Barbier-type propargylation of carbonyl compounds with propargyl bromide has been achieved with reactive zinc-copper couple under solvent-free conditions. The reaction of aldehydes with propargyl bromide produced the unique homopropargyl alcohols in excellent yields at room temperature without the formation of homoallenyl alcohols. The ketones reacted with propargyl bromide to give the corresponding homopropargyl alcohols in good to excellent yields at -14 to -16 °C. The advantages of this method are excellent yields, short reaction time, high regioselectivity, and avoidance of the use of organic solvents.
- Ma, Xiaofang,Wang, Jin-Xian,Li, Shunxi,Wang, Ke-Hu,Huang, Danfeng
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experimental part
p. 8683 - 8689
(2009/12/24)
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- Efficient synthesis of 3-chloromethyl-2(5H)-furanones and 3-chloromethyl- 5,6-dihydropyran-2-ones via the PdCl2-catalyzed chlorocyclocarbonylation of 2,3- or 3,4-allenols
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(Chemical Equation Presented) A mild and efficient methodology involving PdCl2-catalyzed chlorocyclocarbonylation of 2,3- or 3,4-allenols with CuCl2 for the synthesis of 3-chloromethyl-2(5H)-furanones and 3-chloromethyl-5,6-dihydropyran-2-ones was developed. This reaction proceeded in a highly regioselective manner, i.e., the chlorine atom was introduced to the terminal position of the allene moiety while the lactone linkage was formed between the center carbon atom of the allene moiety and the hydroxyl oxygen, which was established by the X-ray single crystal diffraction study of γ-lactone 3p. The highly optically active 3-chloromethyl-2(5H)-furanones could be easily prepared from the readily available optically active 2,3-allenols. A mechanism for this reaction was proposed.
- Cheng, Xin,Jiang, Xuefeng,Yu, Yihua,Ma, Shengming
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supporting information; experimental part
p. 8960 - 8965
(2009/04/11)
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- Ring opening/fragmentation of dihydropyrones for the synthesis of homopropargyl alcohols
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Ring-opening/C-C bond cleavage reactions induced by nucleophilic addition of methyl Grignard to 5,6-dihydro-2-pyrone (DHP) triflates 1 furnish homopropargyl alcohols (1 → 2) stereospecifically with respect to the stereochemistry of 1. Carbonyl extrusion from DHP triflates provides a unified and operationally simple strategy for preparing chiral homopropargyl alcohols. Copyright
- Tummatorn, Jumreang,Dudley, Gregory B.
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p. 5050 - 5051
(2008/10/09)
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- Rhodium(l)-catalyzed carbonyl allenylation versus propargylation via redox transmetalation across tetragonal tin(ll) oxide
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A reagent combination of β-SnO and catalytic [Rh(COD)Cl]2 in THF-H2O promotes the reaction of propargyl bromides and aldehydes and directs the regioselectivity toward the formation of either allenic alcohols or homopropargylic alcohols. This highly regioselective either/or transformation proceeds via a transmetalation from rhodium to tin, in which metallotropic rearrangement between a propargylmetal and allenylmetal is arrested.
- Banerjee, Moloy,Roy, Sujit
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p. 2137 - 2140
(2007/10/03)
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- Highly efficient synthesis of propargyl- and allenyltitanium reagents from propargyl halides or propargyl alcohol derivatives. Practical synthesis of allenyl and homopropargyl alcohols
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Reaction of Ti(O-i-Pr)4/2 i-PrMgBr, synthetic equivalent of practical Ti(II) reagent, with propargyl halides or propargyl alcohol derivatives affords allenyl titanium compounds in excellent yields, thus providing an efficient and practical meth
- Nakagawa, Takashi,Kasatkin, Aleksandr,Sato, Fumie
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p. 3207 - 3210
(2007/10/02)
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- Theonellamide F Synthetic Studies. Stereoselective Synthesis of (3S,4S,5E,7E)-3-Amino-8-(4-bromophenyl)-4-hydroxy-6-methyl-5,7-octadienoic acid (Aboa)
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A convergent stereocontrolled synthesis of (3S,4S,5E,7E)-3-amino-8-(4-bromophenyl)-4-hydroxy-6-methyl-5,7-octadienoic acid (Aboa, 2), a constituent of theonellamide F from a marine sponge, has been achieved.The key steps include the carboalumination of th
- Tohdo, Keisuke,Hamada, Yasumasa,Shioiri, Takayuki
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p. 2031 - 2034
(2007/10/02)
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- Selective Synthesis of Allenic and Acetylenic Derivatives via Pentaorganylstiboranes
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Allenyltetrabutylstiborane (3), formed from allenyltributylstibonium bromide (2) and butylmagnesium bromide, reacted with aldehydes to give homopropargylic alcohols (4) exclusively in excellent yields, while 2-butynyltetrabutylstiborane (6), formed from 2
- Zhang, Li-Jun,Huang, Yao-Zeng,Huang, Zhe-Hui
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p. 6579 - 6582
(2007/10/02)
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- Reaction of Propargyl Bromide with Aldehydes in the Presence of Metallic Tin. Synthesis of Homopropargylalcohols and Homoallenylalcohols
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In the presence of water, metallic tin and propargyl bromide reacted smoothly with aldehydes to give the corresponding homopropargyl alcohols (a) and homoallenyl alcohols (b).High chemospecifity to bifunctional carbonyl compounds containing -OH, -X and -NO2 etc. was obtained.
- Wu, Shihui,Huang, Bangzhou,Gao, Xiang
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p. 1279 - 1286
(2007/10/02)
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- PHENYLENE, FURYL, AND THIENYL LEUKOTRIENE B4 ANALOGUES
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This invention relates to leukotriene B 4 antagonists having the structure STR1 and the pharmaceutically acceptable addition salts thereof; wherein R 1 is lower alkyl having 1-10 carbon atoms; or lower alkenyl or alkynyl having 2-10 carbon atoms; or lower
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