- Manganese-Mediated C-C Bond Formation: Alkoxycarbonylation of Organoboranes
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Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form an ester product containing the target C-C bond. The required organo(alkoxy)borate salts are conveniently generated from the stoichiometric reaction of an organoborane and an alkoxide salt and can be telescoped without purification. The protocol leads to the formation of both aromatic and aliphatic esters and gives complete control over the ester's substitution (e.g., OMe, OtBu, OPh). A reaction mechanism was proposed on the basis of stoichiometric reactivity studies, spectroscopy, and DFT calculations. The new chemistry is particularly relevant for the field of Mn(I) catalysis and clearly points to a potential pathway toward irreversible catalyst deactivation.
- Van Putten, Robbert,Filonenko, Georgy A.,Krieger, Annika M.,Lutz, Martin,Pidko, Evgeny A.
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supporting information
p. 674 - 681
(2021/04/02)
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- Highly regioselective and rapid hydroformylation of alkyl acrylates catalyzed by a rhodium complex with a tetraphosphorus ligand
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Alkyl acrylates have been hydroformylated to the linear aldehydes with high regioselectivity (linear/branch > 99/1) and extraordinarily high average turnover frequencies (up to 5400 h-1) by using a rhodium complex with a tetraphosphorus ligand.
- Yu, Shichao,Chie, Yu-Ming,Zhang, Xumu
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experimental part
p. 537 - 540
(2009/11/30)
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- OXIDATION OF α-DIKETONES BY THE SYSTEM ALUMINUM TRI-tert-BUTYLATE-tert-BUTYL HYDROPEROXIDE
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α-Diketones (butanedione, 2,3-pentanedione, benzil) react with tert-butyl hydroperoxide to form the corresponding anhydrides and tert-butyl alcohol.In the reaction of α-diketones with an oxidative system including aluminum tri-tert-butylate and tert-butyl hydroperoxide, tert-butylacylates and peracylates of the corresponding carboxylic acids are formed as the major reaction products.
- Stepovik, L. P.,Dodonov, V. A.,Smyslova, G. N.
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p. 102 - 106
(2007/10/02)
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- Acylations des cetones α-β-ethyleniques catalysees par les acides sulfoniques : synthese concomitante de sels de pyrylium et de dihydro-2,3-pyrones-4
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The acylation of α,β-ethylenic ketones by carboxylic acid anhydrides catalyzed by sulfonic acids lead to the expected unsymmetrical pyrylium salts. 2,3-Dihydro-pyran-4-ones are also formed.The respective yields depend upon the alkyl substituents of the starting material.
- Graindorge, Herve,Roussel, Christian
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p. 454 - 458
(2007/10/02)
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