Conjugated unsaturated systems electron delocalization

Lycopene is a red pigment found in tomatoes, watermelon, papaya, guava, and pink grapefruit. An antioxidant like vitamin E, lycopene contains many conjugated double bonds—double bonds separated by only one single bond—that allow jt electron density to delocalize and give the molecule added stability. In Chapter 16 we learn about such conjugated unsaturated systems. 

Benzylic radicals and benzylic cations are conjugated unsaturated systems and hoth are unusually stable. They have approximately the same stabilities as allybc radicals (Section 10.8) and allylic cations (Section 13-4). This exceptional stability of benzylic radicals and cations can be explained by resonance theory. In the case of each entity, resonance structures can be written that place either the unpaired electron (in the case of the radical) or the positive charge (in the case of the cation) on an ortho or para carbon of the ring (see the following structures). Thus resonance delocalizes the unpaired electron or the charge, and this delocabzation causes the radical or cation to be highly stabibzed. 

A conjugated unsaturated system is a molecular unit containing tt electrons that can be delocalized over three or more contiguous atoms. 

Aldol condensation offers an effective route to a p unsaturated aldehydes and ketones These compounds have some interesting properties that result from conjugation of the carbon-carbon double bond with the carbonyl group As shown m Figure 18 6 the rr systems of the carbon-carbon and carbon-oxygen double bonds overlap to form an extended rr system that permits increased electron delocalization... 

This electron delocalization stabilizes a conjugated system Under conditions cho sen to bring about their mterconversion the equilibrium between a p 7 unsaturated ketone and an a p unsaturated analog favors the conjugated isomer... 

The meaning of the word aromaticity has evolved as understanding of the special properties of benzene and other aromatic molecules has deepened. Originally, aromaticity was associated with a special chemical reactivity. The aromatic hydrocarbons were considered to be those unsaturated systems that underwent substitution reactions in preference to addition. Later, the idea of special stability became more important. Benzene can be shown to be much lower in enthalpy than predicted by summation of the normal bond energies for the C=C, C—C, and C—H bonds in the Kekule representation of benzene. Aromaticity is now generally associated with this property of special stability of certain completely conjugated cyclic molecules. A major contribution to the stability of aromatic systems results from the delocalization of electrons in these molecules. 

Conjugation of the 7t-electrons of the carbon-carbon double bond with the LUMO sulfur 3d-orbitals would be expected to stabilize the Hiickel 4n -I- 2 (n = 0) array of n-electrons in the thiirene dioxide system. No wonder, therefore, that the successful synthesis of the first member in this series (e.g. 19b) has initiated and stimulated several studies , the main objective of which was to determine whether or not thiirene dioxides should be considered to be aromatic (or pseudo-aromatic ) and/or to what extent conjugation effects, which require some sort of n-d bonding in the conjugatively unsaturated sulfones, are operative within these systems. The fact that the sulfur-oxygen bond lengths in thiirene dioxides were found to be similar to those of other 802-containing compounds, does not corroborate a Hiickel-type jr-delocalization... 

Because conjugation always lowers the energy of an unsaturated system by allowing the TT electrons to be delocalized, this behavior is just what we would expect. 

An interesting case are the a,/i-unsaturated ketones, which form carbanions, in which the negative charge is delocalized in a 5-centre-6-electron system. Alkylation, however, only occurs at the central, most nucleophilic position. This regioselectivity has been utilized by Woodward (R.B. Woodward, 1957 B.F. Mundy, 1972) in the synthesis of 4-dialkylated steroids. This reaction has been carried out at high temperature in a protic solvent. Therefore it yields the product, which is formed from the most stable anion (thermodynamic control). In conjugated enones a proton adjacent to the carbonyl group, however, is removed much faster than a y-proton. If the same alkylation, therefore, is carried out in an aprotic solvent, which does not catalyze tautomerizations, and if the temperature is kept low, the steroid is mono- or dimethylated at C-2 in comparable yield (L. Nedelec, 1974). 

As we have already seen, delocalization of electrons by conjugation decreases the energy difference between the HOMO and LUMO energy levels, and this leads to a red shift. Alkyl substitution on a conjugated system also leads to a (smaller) red shift, due to the small interaction between the cr-bonded electrons of the alkyl group with the K-bond system. These effects are additive, and the empirical Woodward-Fieser rules were developed to predict the 2max values for dienes (and trienes). Similar sets of rules can be used to predict the A ax values for a,P-unsaturated aldehydes and ketones (enones) and the Amax values for aromatic carbonyl compounds. These rules are summarized in Table 2.4. 

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