TAUTOMERISM

SMT. S. J. Varmora Science College, Surendranagar

INTRODUCTION

Tautomerism is a special case of structural isomerism & can play important

role in non-canonical base pairing in DNA & especially RNA molecules.
Tautomerism is isomers of a compound which differ only in the position of
the proton & electron, the carbon skeleton of the compound remains
unchanged. A reaction which involves simple proton transfer in an
intramolecular fashion is called tautomerism.
Common tautomerism pairs :
Keto-enol
Ketene-ynol
Enamine-imine
Amide-imidic
Lactam-lactim

KETO-ENOL TAUTOMERISM

HISTORY

In organic chemistry, keto-enol tautomerism refers to a chemical equilibrium between a keto-form and enol-form. The enol and keto form are said to be
tautomer of each other. The inter conversion of the two forms involves the moment of x-hydrogen and the shifting of bonding electron. Hence, the isotherm
equlities as tautomerism.

One of the early investigators into keto-enol tautomerism was EMILERLENMEYER. His Erlenmeyer rule, developed in 1880.He states that all
alcohols in which the hydroxyl group is attached directly to a c=c atom
become aldehyde and keton. This conversion occurs because the keto form is
in general, more stable that its enol tautomer. The keto form is therefore
favored at equilibrium because it the lower energy forms.

MECHANISM:

A compound containing a carbonyl group (C=C) is normally in rapid equilibrium with an enol tautomer, which contain a pair of doubly bonded carbon atom
adjacent to hydroxyl group, C=C-OH. The keto form predominates at equilibrium for most ketons. Nonetheless, the enol form is important for some
reactions. The deprotonated intermediate in the interconversation of the two forms referred to as an enolate anion is important in carbonyl chemistry, in large
part, because it is a strong neucleophile.
Overall reaction:

Normally, the keto-enol tatutomerization chemical equilibrium highly thermodynamically given an at room temperature equilibrium heavily fever the
formation of the keto forms.

Because of acidity of hydrogen carbonyls undergo tautomerism. Tautomers are rapidly in converted constitutional isomers, usually distinguished by a different
bonding location for a labile hydrogen atom and a differently located double bond. The equilibrium between tautomers is not only rapid under normal
conditions, but it often strongly favors one of the isomers (acetone, for example, is 99.999% keno tautomers). Even in such one-sided equilibrium, evidence for
the presence of the minor tautomer comes from the chemical behavior of the compound. Tautomeric equilibrium is catalyzed by traces of acids or basis that are
generally present in most chemical samples.

BASE CATALZED ENOLIZATION:

However under acidic and basic conditions the equilibrium can be shifted to the right.

ACID CATALYZED ENOLIZATION:

Example of tautomerism:Tautomerism is also occur in nitrogen base, in purine and pyrimidine.

URACIL:
Pyrimidin base uracil also shows tautorisam.
When uracil may be go under tautomerization in charging from the keto
to the enol functionality by intramolecular proton transfer due to rich
electron ring.
KETO-ENOL TAUTOMERISM IN URACIL:

SIGNIFICANCE IN BIOCHEMISTRY:
Keto-enol tautomerism is important in several areas of biochemistry.
The high phosphate-transfer potential of phosphoenolpyruvate results from the fact that the phosphorylated compound is trapped in the less
thermodynamically favorable enol form, whereas after dephosphorylation it can assume the keto form.
Rare enol tautomers of the bases guanine and thymine can lead to mutation because of their altered base pairing properties.
IMPORTANCE OF KETO-ENOL IN DNA
In deoxyribonucleic acid (DNA), the nucleotide bases are in keto form.
However, James Watson & Francis Crick first believed them to be in the enol tautomeric form until corrected by Jerry Donohue. Their mistaker initial
understanding prevented them from solving the structure of DNA until corrected.
REFERENCS:
Investigation into the chemistry of thermodynamically unstable species. The direct polymerization of vinyl alcohol, the enolic tautomer of acetaldehyde.
ANNA K. CEDERASTAVE & BRUCE M. NOVAK. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,1994,volume 116,pages 407374.[1]

Mechanism

Rediscovery, isolation, & Asymmetric reduction of 1,2,3,4-tetrahydronaphthalene-1,4-dione and study of its [Cr(CO)3] complex E.PETER KUNDIG ,
ALVARO ENRIQUEZ GARCIA , THIERRY LOMVERGET , GERALD BERNARDINELLI ANGEWANDTE CHEMIE INTERNATIONAL

EDITION volume 45, issue 1, pages 98-101 2006 abstract

THYMIN:
Thymine exists in two tautomeric forms the keto & the enol form, where
the keto form is strongly forward in the equilibrium.

WANG, W. H. W. HELLINGA, et al. (2011). Structural evidence for the rare tautomer hypothesis of spontaneous mutagenesis. Proceedings of the
national academy of science 108(43):17644-17648.
The Eighth day of creation. JUDSON, HORANCE FREELAND.SIMON & SCHUSTER, NY:1979.