- Copper-Catalyzed Synthesis of Terminal vs. Fluorine-Substituted N-Allenamides via Addition of Diazo Compounds to Terminal Ynamides
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A copper-mediated coupling reaction between ynamides and diazo-compounds to produce N-allenamides is reported for the first time. This method enables facile and rapid access to terminal N-allenamides by using commercially available TMS-diazomethane with w
- Zheng, Yongxiang,Moegle, Baptiste,Ghosh, Santanu,Perfetto, Anna,Luise, Davide,Ciofini, Ilaria,Miesch, Laurence
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supporting information
(2021/12/14)
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- Regioselective 1,2-addition of allenamides with: N -haloimides: Synthesis of 2-halo allylic aminal derivatives
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A strategy for the synthesis of 2-halo allylic aminal derivatives through regioselective 1,2-addition of allenamides with N-haloimides is presented. This reaction was conducted under very mild conditions and gave up to 99% yield. Moreover, the obtained ha
- Li, Hong-He,Li, Xiao-Xiao,Zhao, Zhi-Gang,Yuan, Xiao,Sun, Chen-Yang
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p. 4005 - 4013
(2017/07/11)
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- Enantioselective Oxidative (4+3) Cycloadditions between Allenamides and Furans through Bifunctional Hydrogen-Bonding/Ion-Pairing Interactions
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BINOL-based N-trifluoromethanesulfonyl phosphoramides catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. The chiral organic phosphoramide counteranion is proposed to engage in the activation of the oxyallyl cation intermediate through cooperative hydrogen-bonding and ion-pairing interactions, enabling an efficient chirality transfer that provide the final adducts with high diastereo- and enantioselectivities. Remarkably, the reaction shows a wide substrate scope that includes a variety of substituted allenamides and furans.
- Villar, Laura,Uria, Uxue,Martínez, Jose I.,Prieto, Liher,Reyes, Efraim,Carrillo, Luisa,Vicario, Jose L.
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supporting information
p. 10535 - 10538
(2017/08/22)
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- Gold-catalyzed [3+2]-annulations of α-aryl diazonitriles with ynamides and allenamides to yield 1-amino-1H-indenes
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Gold-catalyzed [3+2]-annulations of α-aryl diazonitriles with ynamides and allenamides yield 1-amino-1H-indenes in two distinct pathways; the success of these annulations relies on the high electrophilicity of α-cyano arylgold carbenes to activate an ionic pathway.
- Singh, Rahulkumar Rajmani,Pawar, Samir Kundlik,Huang, Min-Jie,Liu, Rai-Shung
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supporting information
p. 11434 - 11437
(2016/09/23)
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- Regioselective Alkylative Carboxylation of Allenamides with Carbon Dioxide and Dialkylzinc Reagents Catalyzed by an N-Heterocyclic Carbene–Copper Complex
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The alkylative carboxylation of allenamide catalyzed by an N-heterocyclic carbene (NHC)–copper(I) complex [(IPr)CuCl] with CO2and dialkylzinc reagents was investigated. The reaction of allenamides with dialkylzinc reagents (1.5 equiv) and CO2(1 atm.) proceeded smoothly in the presence of a catalytic quantity of [(IPr)CuCl] to afford (Z)-α,β-dehydro-β-amino acid esters in good yields. The reaction is regioselective, with the alkyl group introduced onto the less hindered γ-carbon, and the carboxyl group introduced onto the β-carbon atom of the allenamides. The first step of the reaction was alkylative zincation of the allenamides to give an alkenylzinc intermediate followed by nucleophilic addition to CO2. A variety of cyclic and acyclic allenamides were found to be applicable to this transformation. Dialkylzinc reagents bearing β-hydrogen atoms, such as Et2Zn or Bu2Zn, also gave the corresponding alkylative carboxylation products without β-hydride elimination. The present methodology provides an easy route to alkyl-substituted α,β-dehydro-β-amino acid ester derivatives under mild reaction conditions with high regio- and stereoselectivtiy.
- Gholap, Sandeep Suryabhan,Takimoto, Masanori,Hou, Zhaomin
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supporting information
p. 8547 - 8552
(2016/07/07)
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- A simple one-pot preparation of N-allenyl amides, ureas, carbamates and sulfonamides using a DMSO/tBuOK protocol
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A one-pot transformation of amides, ureas, carbamates and sulfonamides into synthetically useful N-allenyl analogues using a tBuOK/DMSO protocol is reported. The procedure is experimentally simple and robust, and provides N-allenyl analogues, c
- Bousfield, Thomas W.,Kimber, Marc C.
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p. 350 - 352
(2015/03/18)
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- An intermolecular hydroamination of allenamides with arylamines catalyzed by cationic Au(I) salts
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(Figure presented) An intermolecular hydroamination of allenamides with arylamines has been achieved under mild Au(I) catalysis conditions delivering allylamino E-enamides stereoselectively and in high yield. The reaction is made possible via a convenient method for conjugated N-acyliminium formation.
- Hill, Anthony W.,Elsegood, Mark R. J.,Kimber, Marc C.
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scheme or table
p. 5406 - 5409
(2010/10/02)
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- A facile and mild synthesis of enamides using a gold-catalyzed nucleophilic addition to allenamides
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Chemical Equation Presentation A mild and facile synthesis of enamides has been developed, based on nucleophilic addition of electron-rich aromatic and heteroaromatics to an allenamide unit catalyzed by a gold salt. Yields for the transformation were 29-98%.
- Kimber, Marc C.
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scheme or table
p. 1128 - 1131
(2010/06/11)
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- Efficient preparations of novel ynamides and allenamides
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Practical syntheses of a series of novel ynamides and allenamides are described here. While a base-induced isomerization protocol of propargyl amides leads to an array of chiral and achiral allenamides, ynamides are prepared from enamides via bromination followed by base-induced elimination of the Z-bromoenamides. These ynamides and allenamides possess improved thermal stability compared to ynamines and allenamines. They can be isolated, purified, and handled with ease, and thus, should be synthetically more useful than traditional ynamines and allenamines.
- Wei, Lin-Li,Mulder, Jason A.,Xiong, Hui,Zificsak, Craig A.,Douglas, Christopher J.,Hsung, Richard P.
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p. 459 - 466
(2007/10/03)
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- Inverse demand [4+2] cycloaddition reactions of allenamides: Reactivity scopes of an electron deficient variant of allenamines
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The synthesis and reactivity of a series of new allenamides are described. These electron deficient variants of allenamines are more stable than allenamines but possess comparable reactivity. Particularly, oxazolidinone and imidazolidinone substituted allenamides undergo efficient inverse demand [4+2] cycloaddition reactions with heterodienes, leading to unique pyranyl heterocycles. The reactivity differences between various allenamides containing different substitution patterns around the nitrogen atom are illustrated.
- Wei, Lin-Li,Xiong, Hui,Douglas, Christopher J.,Hsung, Richard P.
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p. 6903 - 6907
(2007/10/03)
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