- Iridium-Catalyzed Enantioselective Unbiased Methylene C(sp3)–H Borylation of Acyclic Amides
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We herein report amide directed enantioselective β-C(sp3)?H borylation of unbiased methylene C?H bonds of acyclic amides enabled by iridium catalysis for the first time. The key to the success of this transformation relies on the careful select
- Yang, Yuhuan,Chen, Lili,Xu, Senmiao
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supporting information
p. 3524 - 3528
(2020/12/15)
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- Chemo- and Stereoselective Transition-Metal-Free Amination of Amides with Azides
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The synthesis of α-amino carbonyl/carboxyl compounds is a contemporary challenge in organic synthesis. Herein, we present a stereoselective α-amination of amides employing simple azides that proceeds under mild conditions with release of nitrogen gas. The
- Tona, Veronica,De La Torre, Aurélien,Padmanaban, Mohan,Ruider, Stefan,González, Leticia,Maulide, Nuno
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supporting information
p. 8348 - 8351
(2016/07/26)
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- Catalytic acylation of amines with aldehydes or aldoximes
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The simple nickel salt NiCl2?6H2O catalyzes the coupling of aldoximes with amines to give secondary or tertiary amide products. The aldoxime can be prepared in situ from the corresponding aldehyde. The use of 18O-labeled oximes has allowed insight into the mechanism of this reaction.
- Allen, C. Liana,Davulcu, Simge,Williams, Jonathan M. J.
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supporting information; experimental part
p. 5096 - 5099
(2011/02/21)
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- Reactions of aryl phenylacetates with secondary amines in MeCN. Structure-reactivity relationship in the ketene-forming eliminations and concurrent E2 and E1cb mechanisms
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Elimination reactions of aryl esters of arylacetic acids 1 and 2 promoted by R2NH in MeCN have been investigated kinetically. The reactions are second-order and exhibit β = 0.44-0.84, β(lg) = 0.41-0.50, and ρ(H) = 2.0-3.6. Bronsted β and β(lg) decrease with the electron-withdrawing ability of the β-aryl substituent. Hammett ρ(H) values remain nearly the same, but the β(lg) value increases as the base strength becomes weaker. Both ρ(H) and β decrease with the change of the leaving group from 4-nitrophenoxide to 2,4-dinitrophenoxide. The results are consistent with an E2 mechanism and a reaction coordinate with a large horizontal component corresponding to proton transfer. When the base-solvent system is changed from R2NH-MeCN to R2NH/R2NH2+-70 mol% MeCN(aq), the Bronsted β, ρ(H), and β(lg) decrease. Finally, the ketene-forming elimination reactions from p-nitrophenyl p-nitrophenylacetate promoted by R2NH/R2NH2+ buffers in 70 mol% MeCN(aq) have been shown to proceed by concurrent E2 and E1cb mechanisms.
- Cho, Bong Rae,Kim, Yong Kwan,Yoon, Choon-Ock Maing
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p. 691 - 697
(2007/10/03)
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