- Palladium-catalyzed intermolecular alkene carboacylation via ester C-O bond activation
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We report palladium-catalyzed intermolecular carboacylation of alkenes with ester electrophiles and tetraarylborate nucleophiles. Bicyclic alkenes react with a variety of pentafluorophenyl benzoate and alkanoate esters and sodium tetraarylborates to form ketone products in ≤99% yields. These reactions occur in the absence of a directing group and demonstrate esters are competent acyl electrophiles for intermolecular alkene carboacylation reactions.
- Banovetz, Haley K.,Vickerman, Kevin L.,David, Colton M.,Alkan, Melisa,Stanley, Levi M.
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p. 3507 - 3512
(2021/05/10)
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- Fluoride anion-initiated bis-trifluoromethylation of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane
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The fluoride anion-initiated reaction of phenyl aromatic carboxylates with (trifluoromethyl)trimethylsilane (Me3SiCF3) that results in the formation of O-silyl-protected 2-aryl-1,1,1,3,3,3-hexafluoroisopropanols is reported. A phenoxide anion, generated during the trifluoromethylation of the phenyl carboxylate, also activates the Me3SiCF3, which permits a catalytic amount of the fluoride anion source to be used. Various functional groups, which can be used for further elaboration, are tolerated in the reaction.
- Takahashi, Kenjiro,Ano, Yusuke,Chatani, Naoto
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supporting information
p. 11661 - 11664
(2020/10/19)
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- Transesterification for synthesis of carboxylates using aldehydes as acyl donors via C-H and C-O bond activations
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A new type of transesterification between aryl, heteroaryl, alkyl N-heteroarene-2-carboxylates and various aldehydes by C-H and C-O bond activations has been developed for the synthesis of versatile carboxylates. A possible mechanism containing oxidative addition of acyl-O bond in parent ester and radical cleavage of sp2 C-H bond in aldehyde is proposed.
- Bao, Yong-Sheng,Chen, Chao-Yue,Huang, Zhi-Zhen
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p. 8344 - 8349,6
(2020/10/15)
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- Self-replicating molecules: A second generation
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The use of self-complementary structures in replication experiments is discussed, and a second generation of self-replicating molecules is introduced. Key design elements of the new system are described, specifically a high affinity (Ka ~ 105 M-1 in CDCl3) between the two complementary reactive components and the careful placement of nucleophilic and electrophilic centers within the system. These considerations preclude intramolecular reactions within two-component complexes, thus minimizing undesirable background reactions. Autocatalysis is observed in the new systems, and by using appropriate control experiments the autocatalysis is traced to template effects.
- Wintner, Edward A.,Conn, M. Morgan,Rebek Jr., Julius
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p. 8877 - 8884
(2007/10/02)
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