7218-49-7Relevant academic research and scientific papers
One-Carbon Homologation of Primary Alcohols to Carboxylic Acids, Esters, and Amides via Mitsunobu Reactions with MAC Reagents
Kagawa, Natsuko,Nibbs, Antoinette E.,Rawal, Viresh H.
, p. 2363 - 2366 (2016/06/09)
A method is reported for the one-carbon homologation of an alcohol to the extended carboxylic acid, ester, or amide. The process involves the Mitsunobu reaction with an alkoxymalononitrile, followed by unmasking in the presence of a suitable nucleophile. The homologation and unmasking can even be performed in a one-pot process in high yield.
Ni-catalyzed direct carboxylation of benzyl halides with CO2
León, Thierry,Correa, Arkaitz,Martin, Ruben
supporting information, p. 1221 - 1224 (2013/03/14)
A novel Ni-catalyzed carboxylation of benzyl halides with CO2 has been developed. The described carboxylation reaction proceeds under mild conditions (atmospheric CO2 pressure) at room temperature. Unlike other routes for similar means, our method does not require well-defined and sensitive organometallic reagents and thus is a user-friendly and operationally simple protocol for assembling phenylacetic acids.
A new synthesis of β,γ-alkenyl carboxylic acids from α,β-alkenyl carboxylic acid chlorides and α,β-alkenyl aldehydes with one-carbon elongation
Satoh, Tsuyoshi,Nakamura, Akira,Iriuchijima, Atsuko,Hayashi, Yasumasa,Kubota, Ko-Ichi
, p. 9689 - 9696 (2007/10/03)
Reaction of the lithium α-sulfinyl carbanion of chloromethyl phenyl sulfoxide with α,β-alkenyl carboxylic acid chlorides gave γ,δ-alkenyl α-chloro-β-keto sulfoxides in variable yields. The keto sulfoxides were also synthesized from α,β-alkenyl aldehydes in two steps in good overall yields: addition of the lithium α-sulfinyl carbanion of chloromethyl phenyl sulfoxide to α,β-alkenyl aldehydes followed by oxidation of the adducts with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone or Dess-Martin periodinane. These products were treated in sequence with potassium hydride, tert-butyllithium, and 5% aqueous sodium hydroxide, in one flask to give β,γ-alkenyl carboxylic acids with one-carbon elongation in good yields. The procedure offers a new method for synthesizing β,γ-alkenyl carboxylic acids from α,β-alkenyl carboxylic acid chlorides and α,β-alkenyl aldehydes with one-carbon elongation.
Correlation of rates of uncatalyzed and hydroxide-ion catalyzed ketene hydration. A mechanistic application and solvent isotope effects on the uncatalyzed reaction
Andraos, John,Kresge, A. Jerry
, p. 508 - 515 (2007/10/03)
Rates of hydration of a number of ketenes were measured in neutral and basic solution using flash photolytic techniques, and rate constants for their uncatalyzed, k(uc), and hydroxide-ion catalyzed, k(HO), reactions were determined. These results, plus additional data from the literature, were found to provide the remarkably good correlation log k(uc) = -3.21 + 1.14 log k(HO), which spans 10 orders of magnitude in reactivity and includes 31 ketenes. This good correlation implies that uncatalyzed and hydroxide-ion catalyzed ketene hydraton occur by similar reaction mechanisms, which for the hydroxide-ion catalyzed process is known to involve nucleophilic attack on the carbonyl carbon atom of the ketene. Rate constants for phenylhydroxyketene, on the other hand, do not fit this correlation, which suggests that the mechanistic assignment upon which these rate constants are based may not be correct. Solvent isotope effects on these uncatalyzed ketene hydrations are weak; most are less than k(H)/k(D) = 2. It is argued that these isotope effects are largely, if not entirely, secondary in nature and that they are consistent with both a reaction mechanism in which nucleophilic attack of a single water molecule on the ketene carbonyl carbon atom produces a zwitterionic intermediate and also a mechanism that avoids this intermediate by passing through a cyclic transition state involving several water molecules.
