Vinylogy

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Vinylogy is the transmission of electronic

effects through a conjugated organic
bonding system.[1] The concept was
introduced in 1926 by Ludwig Claisen to
explain the acidic properties of
formylacetone and related
ketoaldehydes.[2] Its adjectival form,
vinylogous, is used to describe functional
groups in which the standard moieties of
the group are separated only by a
conjugated bonded system. For example,
a carbon-carbon double bond (>C=C<, a
"vinyl" moiety) between a carbonyl group
and a hydroxyl group is referred to as a
vinylogous carboxylic acid, analogous
electronically to a carboxylic acid, RCOOH.

Delocalization of negative charge in a generic

carboxylate anion, derived from an organic carboxylic
acid (cf. acetic acid), and the corresponding vinylogous
carboxylate anion (the "vinylog/vinylogue" of the
carboxylate anion) where a vinyl group now separates
carboxylate anion), where a vinyl group now separates
the charged oxygen from the carbonyl (>C=O) group.
The validity of the theoretical concept of vinylogy is
supported by the pKa of such vinylogs, which approach
that of the analogous carboxylic acid.

Vinylogous reactivity
Vinylogous reactions are believed to occur
when orbitals of the double bonds of the
vinyl group and of an attached electron-
withdrawing group (EWG; the π orbitals)
are aligned and so can overlap and mix
(i.e., are conjugated). Electron
delocalization enables the EWG to receive
electron density through participation of
the conjugated system. Vinylogous
reactions also include conjugate additions,
where a nucleophile reacts at the vinyl
terminus, as well as a vinylogous variation
of the aldol reaction, where an electrophile
is attacked by a nucleophilic vinylogous
enolate (see first and following image).
The vinylogous enolate reacts at the
terminal position of the double bond
system (the γ-carbon), rather than the α-
carbon immediately adjacent to the
carbonyl, as would a simple enolate. Allylic
electrophiles often react by vinylogous
attack of a nucleophile rather than direct
addition.
Vinylogous Aldol Reaction. Cf. the simple aldol
reaction.

A further example of vinylogous reactivity:

ascorbic acid (Vitamin C) behaves as a
vinylogous carboxylic acid by involvement
of its carbonyl moiety, a vinyl group within
the ring, and the lone pair on the hydroxyl
group acting as the conjugated system.
Acidity of the hydroxyl proton at the
terminus of the vinyl group in ascorbic
acid is more comparable to a typical
carboxylic acid than an alcohol because
two major resonance structures stabilize
the negative charge on the conjugate base
of ascorbic acid (center and right
structures in last image), analogous to the
two resonance structures that stabilize the
negative charge on the anion that results
from removal of a proton from a simple
carboxylic acid (cf. first image).

Electron pushing for major resonance structures in

conjugate base of ascorbic acid

References
1. The Vinylogous Aldol Reaction: A
Valuable, Yet Understated Carbon-
Carbon Bond-Forming Maneuver
Giovanni Casiraghi, Franca Zanardi,
Giovanni Appendino, and Gloria Rassu
Chem. Rev. 2000; 100(6) pp 1929 -
1972; (Review)
doi:10.1021/cr990247i
2. Zu den O-Alkylderivaten des Benzoyl-
acetons und den aus ihnen
entstehenden Isoxazolen. (Entgegnung
an Hrn. O. Weygand.) Berichte der
deutschen chemischen Gesellschaft
(A and B Series) Volume 59, Issue 2,
Date: 10. February 1926, Pages: 144-
 153 L. Claisen.
doi:10.1002/cber.19260590206

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