- 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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p. 1060 - 1065
(2021/02/16)
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- Allenone-Mediated Racemization/Epimerization-Free Peptide Bond Formation and Its Application in Peptide Synthesis
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Allenone has been identified as a highly effective peptide coupling reagent for the first time. The peptide bond was formed with an α-carbonyl vinyl ester as the key intermediate, the formation and subsequent aminolysis of which proceed spontaneously in a racemization-/epimerization-free manner. The allenone coupling reagent not only is effective for the synthesis of simple amides and dipeptides but is also amenable to peptide fragment condensation and solid-phase peptide synthesis (SPPS). The robustness of the allenone-mediated peptide bond formation was showcased incisively by the synthesis of carfilzomib, which involved a rare racemization-/epimerization-free N to C peptide elongation strategy. Furthermore, the successful synthesis of the model difficult peptide ACP (65-74) on a solid support suggested that this method was compatible with SPPS. This method combines the advantages of conventional active esters and coupling reagents, while overcoming the disadvantages of both strategies. Thus, this allenone-mediated peptide bond formation strategy represents a disruptive innovation in peptide synthesis.
- Wang, Penghui,Wang, Xuewei,Wang, Zhengning,Zhao, Junfeng
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p. 10374 - 10381
(2021/07/26)
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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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p. 1727 - 1731
(2020/03/13)
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- Synthesis of Acyl Alkenylindium Reagents and Their Application in the Synthesis of (Z)-α,β-Unsaturated Ketones via Palladium-Catalyzed Cross-Coupling Reaction
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A synthetic method for the preparation of acyl alkenylindium reagents was developed involving the hydroindation reaction of allenyl ketones with indium and indium chloride in methanol under mild conditions. Their synthetic applications were demonstrated from Pd-catalyzed cross-coupling reactions with aryl bromides and iodides and alkenyl and aryl triflates for the synthesis of (Z)-α,β-unsaturated ketones.
- Park, Youngchul,Min, Jiae,Eom, Dahan,Lee, Phil Ho
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supporting information
p. 3934 - 3937
(2015/08/19)
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- Sustainable and selective synthesis of 3,4-dihydroquinolizin-2-one and quinolizin-2-one derivatives via the reactions of penta-3,4-dien-2-ones
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In this paper, a novel and green methodology for the synthesis of 3,4-dihydroquinolizin-2-one derivatives via the tandem reactions of penta-3,4-dien-2-ones with pyridine, quinoline, or isoquinoline at rt in aqueous ethanol was developed. Notably, the reac
- Fan, Xuesen,He, Yan,Zhang, Xinying,Wang, Jianji
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p. 1393 - 1398
(2014/03/21)
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- One-pot cascade reactions of 1-arylpenta-3,4-dien-2-ones leading to 2-arylphenols and dibenzopyroanones
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A one-pot cascade reaction of 1-arylpenta-3,4-dien-2-ones with activated ketones allowed for an efficient and sustainable synthesis of 2-arylphenols. Moreover, this reaction was also found to be compatible and combinable with Pd-catalyzed C-H activation a
- He, Yan,Zhang, Xinying,Fan, Xuesen
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p. 14968 - 14970
(2014/12/11)
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- Gold-catalyzed regioselective synthesis of 2- and 3-alkynyl furans
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Chemical Matching: C2- or C3-alkynylated furans were selectively synthesized by using gold catalysis. Direct C-H alkynylation of furans was achieved with C2 selectivity, and a domino cyclization/alkynylation process starting from allenes gave C3-alkynylat
- Li, Yifan,Brand, Jonathan P.,Waser, Jerome
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p. 6743 - 6747
(2013/07/26)
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- Studies on the Himbert intramolecular arene/allene diels-alder cycloaddition. Mechanistic studies and expansion of scope to all-carbon tethers
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The unusual intramolecular arene/allene cycloaddition described 30 years ago by Himbert permits rapid access to strained polycyclic compounds that offer great potential for the synthesis of complex scaffolds. To more fully understand the mechanism of this
- Schmidt, Yvonne,Lam, Jonathan K.,Pham, Hung V.,Houk,Vanderwal, Christopher D.
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supporting information
p. 7339 - 7348
(2013/06/27)
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- Synthesis of 1,2-allenic ketones through oxidation of homopropargyl alcohols with CrO3(cat.)/TBHP under MWI
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A CrO3 catalyzed oxidation of homopropargyl alcohols with tert-butyl hydroperoxide under microwave irradiation was found to be an efficient and rapid alternative for the preparation of 1,2-allenic ketones. The advantages of this procedure inclu
- Zhang, Xin Ying,Qu, Ying Ying,Wang, Yang Yang,Fan, Xue Sen
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experimental part
p. 268 - 271
(2012/01/30)
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- Ru(III)-catalyzed oxidation of homopropargyl alcohols in ionic liquid: an efficient and green route to 1,2-allenic ketones
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An efficient and environmentally benign synthesis of 1,2-allenic ketones via RuCl3-catalyzed oxidation of homopropargyl alcohols in ionic liquid with tert-butyl hydroperoxide (TBHP) as the oxidant was reported for the first time. With its reasonable efficiency and green nature, this oxidation provides a novel alternative route to 1,2-allenic ketones.
- Fan, Xuesen,Qu, Yingying,Wang, Yangyang,Zhang, Xinying,Wang, Jianji
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scheme or table
p. 2123 - 2126
(2010/06/14)
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- Allenyl ketones as versatile Michael acceptors for the addition of chelated enolates
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Chelated amino acid ester enolates undergo clean 1,4-addition towards allenyl ketones 9, giving rise to unsaturated δ-keto amino acid esters 12 at low temperature. If the reaction is allowed to warm to room temperature, the enolate intermediates A undergo
- Lucas, Simon,Kazmaier, Uii
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p. 255 - 258
(2007/10/03)
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- C-C-Bond Formation by the Palladium-Catalyzed Cycloisomerization/Dimerization of Terminal Allenyl Ketones: Selectivity and Mechanistic Aspects
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The scope of the palladium-catalyzed cyclization/dimerization of terminal allenyl ketones 1 to the 2,4-disubstituted furans 3 has been investigated. Simplified and improved conditions almost exclusively provided the dimer 3, accompanied by only traces of the easily separable monomer 2. The formation of an isomer of 3, the unconjugated ketone 4, was completeley suppressed. Under these mild conditions, besides the normal functional group tolerance known for palladium-catalyzed reactions, an interesting selectivity was observed with functional groups that are known to react either in palladium-catalyzed reactions or reactions catalyzed by other transition-metals. Thus aryl halides, terminal alkynes, 1,6-enynes, and α-allenic alcohols were tolerated. In the latter example the selective reaction of only one out of two different allenes was achieved. Mechanistic investigation indicated a Pd(II)/Pd(IV)-cycle involving palladium(II)-γ-alkoxyvinylcarbene and furylpalladium(IV) hydride intermediates, although a second pathway for the formation of the dimer 3 which also involves Pd(IV)-intermediates like the 3,4-dimethylenepalladacyclopentane 23 and the 3-methylenepalladacyclobutane-like structure 15 (respectively 25) could not completely be excluded.
- Hashmi, A. Stephen K.,Ruppert, Thorsten L.,Knoefel, Thomas,Bats, Jan W.
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p. 7295 - 7304
(2007/10/03)
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