Intramolecular acid-catalyzed amide isomerization in aqueous solution.
نویسندگان
چکیده
[reaction: see text] We report for the first time that stoichiometric and even catalytic quantities of weak acids in aqueous solution can very efficiently catalyze amide isomerization in a carefully designed system in which a proton donor is situated so that intramolecular hydrogen bonding to the amide nitrogen is highly favored. Our results provide the first experimental verification that hydrogen bond donation to the amide nitrogen by charged proton donors may play a very significant role in the enzymatic catalysis of amide isomerization.
منابع مشابه
Intramolecular Catalysis of Amide Isomerization: Kinetic Consequences of the 5-NH- -Na Hydrogen Bond in Prolyl Peptides
The presence of an intramolecular hydrogen bond has been proposed to play a key role in the catalysis of amide isomerization by peptidylprolyl isomerases (PPIases), which are highly conserved and ubiquitous rotamase enzymes that catalyze the cis-trans isomerization of proline residues in peptides and proteins. We present herein kinetic and spectroscopic evidence that indicates the existence of ...
متن کاملStrong Hydrogen Bonding to the Amide Nitrogen Atom in an "Amide Proton Sponge": Consequences for Structure and Reactivity
The carbonyl oxygen atom of the amide functional group is universally believed to be the thermodynamically preferred site of protonation in amides;[1] however, N protonation has been proposed to play a key role in biologically important reactions of peptides and proteins such as acid-catalyzed peptide hydrolysis[2] and cis ± trans isomerization about the CÿN bond.[3] Extensive research into the...
متن کاملPalladium-catalyzed intramolecular delta-lactam formation of aryl halides and amide-enolates: syntheses of cherylline and latifine.
[reaction: see text] Palladium-catalyzed intramolecular carbon-carbon bond formation of aryl halides and amide-enolates gave 4-arylisoquinoline derivatives in good yields, which were further converted into the isoquinoline alkaloids cherylline and latifine.
متن کاملLewis acid-catalyzed redox-neutral amination of 2-(3-pyrroline-1-yl)benzaldehydes via intramolecular [1,5]-hydride shift/isomerization reaction
Lewis acid-catalyzed redox-neutral amination of 2-(3-pyrroline-1-yl)benzaldehydes via intramolcular [1,5]-hydride shift/isomerization reaction has been realized, using the inherent reducing power of 3-pyrrolines. A series of N-arylpyrrole containing amines are obtained in high yields.
متن کاملDetermination of Kinetic Parameters for Catalytic Isomerization of Glucose to Fructose by immobilized Glucose Isomerase in an Aqueous-Ethanol Medium
Catalytic isomerization of glucose to fructose by immobilized glucose isomerase in an aqueous-ethanol medium was studied. Using Michaelis-Menten equation and Haldane relationship, the main kinetic parameters were determined: Kmf, Vmf, Kmr, Vmr. By comparing the aqueous-ethanol medium with an aqueous solution, the measured values of Kmr and Kmf were increased in the aqueous-ethanol solution, whi...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Organic letters
دوره 1 5 شماره
صفحات -
تاریخ انتشار 1999