Carboxylic acid participation in amide hydrolysis. Competition between acid-catalyzed dehydration and anhydride formation

1989 ◽  
Vol 111 (15) ◽  
pp. 5921-5925 ◽  
Author(s):  
Ronald Kluger ◽  
John C. Hunt
Keyword(s):  
Carboxylic Acid ◽  
Amide Hydrolysis ◽  
Acid Catalyzed

Trifluoroacetic acid catalyzed highly regioselective bromocyclization of styrene-type carboxylic acid

2016 ◽  
Vol 14 (20) ◽  
pp. 4571-4575 ◽  
Author(s):  
Tao Chen ◽  
Ying-Yeung Yeung
Keyword(s):  
Carboxylic Acid ◽  
Trifluoroacetic Acid ◽  
Acid Catalyzed

A trifluoroacetic acid catalyzed highly 6-endo regioselective bromocyclization of styrene-type carboxylic acid has been developed.

The Theodorakis Synthesis of (–)-Jiadifenolide

2015 ◽  
Author(s):  
Douglass F. Taber
Keyword(s):  
Hydrogen Peroxide ◽  
Carboxylic Acid ◽  
Aldol Condensation ◽  
University Of California ◽  
Oxidative Rearrangement ◽  
Promote Neurite Outgrowth ◽  
Starting Point ◽  
Jones Reagent ◽  
Acid Catalyzed ◽  
The University

There has recently been a great deal of interest in the synthesis of natural products that promote neurite outgrowth. Emmanuel A. Theodorakis of the University of California, San Diego described (Angew. Chem. Int. Ed. 2011, 50, 3672) the preparation of one of the most potent (10 nM) of these, (–)-jiadifenolide 3. Fittingly, a key transformation en route to this highly oxygenated seco-prezizaane was the oxidative rearrangement of 1 to 2. The starting point for the synthesis was the commercially available diketone 4. Allylation followed by addition to 5 gave the prochiral triketone 6. Enantioselective aldol condensation following the Tu/Zhang protocol then delivered the bicyclic enone 7. Alkylation to give 8 proceeded with high diastereoselectivity, perhaps controlled by the steric bulk of the silyloxy group. Exposure of the protected ketone to the McMurry reagent PhNTf2 gave the enol triflate 9, which smoothly carbonylated to the lactone 10. Epoxidation with alkaline hydrogen peroxide followed by oxidation gave the carboxylic acid, which spontaneously opened the epoxide, leading to the bis lactone 1. With 1 in hand, the stage was set for the key oxidative rearrangement to 2. It was envisioned that epoxidation would generate the cis-fused 11, which on oxidation would undergo acid-catalyzed elimination to give 12. The newly freed OH would then be in position to engage the lactone carbonyl, leading to 2. In the event, oxidation of the epoxide with the Dess-Martin reagent required sonication for 2 h. The rearranged lactone, even though it was susceptible to further oxidation, was secured in 38% overall yield from 1. After hydrogenation and protection, preparation of the enol triflate 13 from the congested cyclopentanone necessitated the use of the more reactive Comins reagent. Hydrogenation of the trisubstituted alkene from coupling with Me3Al then required 90 atmospheres of H2 overpressure. Hydroxylation of the lactone 14 with the Davis oxaziridine followed by further oxidation to the ketone with the Jones reagent and deprotection then completed the synthesis of (–)-jiadifenolide 3.

Dehydrogenation of Alcohols to Carboxylic Acid Catalyzed by in Situ-Generated Facial Ruthenium-CPP Complex

2019 ◽  
Vol 84 (14) ◽  
pp. 9151-9160 ◽  
Author(s):  
Hui-Min Liu ◽  
Lei Jian ◽  
Chao Li ◽  
Chun-Chun Zhang ◽  
Hai-Yan Fu ◽  
...  
Keyword(s):  
Carboxylic Acid ◽  
Acid Catalyzed

Isocarbostyrils. II. The Conversion of 2-Methyl-4-acyl-5-nitroisocarbostyrils to 2-Substituted Indole-4-carboxylic Acids

1971 ◽  
Vol 49 (17) ◽  
pp. 2797-2802 ◽  
Author(s):  
D. E. Horning ◽  
G. Lacasse ◽  
J. M. Muchowski
Keyword(s):  
Sulfuric Acid ◽  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Alkaline Hydrolysis ◽  
Mannich Reaction ◽  
Reductive Cyclization ◽  
Acid Catalyzed ◽  
Acid Anhydrides ◽  
Hydrolysis Of ◽  
Derivatives Of

The sulfuric acid catalyzed acylation of 2-methyl-5-nitroisocarbostyril with carboxylic acid anhydrides gave the corresponding 4-acylated derivatives 3, which underwent reductive cyclization to 2-substituted derivatives of 4-methyl-1,3,4,5-tetrahydropyrrolo[4.3.2.de]isoquinolin-5-one (4). Alkaline hydrolysis of the six-membered lactam in 4 was accompanied by a retro-Mannich reaction to produce 2-substituted indole-4-carboxylic acids in about 40 % overall yield from 3.

Acid-catalyzed Facile Racemization of Axially Dissymmetric 2′-Hydroxy-1,1′-binaphthyl-2-carboxylic Acid

1993 ◽  
Vol 22 (1) ◽  
pp. 79-80 ◽  
Author(s):  
Shuichi Oi ◽  
Kazumasa Kawagoe ◽  
Sotaro Miyano
Keyword(s):  
Carboxylic Acid ◽  
Acid Catalyzed
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