Hydrogen bonding aldehydes

Griesbeck, A.G. and Bondock, S. (2001) Paterno-Biichi reactions of allylic alcohols and acetates with aldehydes hydrogen-bond interaction in the excited singlet and triplet states Journal of the American Chemical Society, 123 (25), 6191-6192. 

In general aldehydes and ketones have higher boiling points than alkenes because they are more polar and the dipole-dipole attractive forces between molecules are stronger But they have lower boiling points than alcohols because unlike alcohols two carbonyl groups can t form hydrogen bonds to each other... 

The carbonyl oxygen of aldehydes and ketones can form hydrogen bonds with the pro tons of OH groups This makes them more soluble m water than alkenes but less solu ble than alcohols... 

Hydrogen bonding m carboxylic acids raises their melting points and boiling points above those of comparably constituted alkanes alcohols aldehydes and ketones... 

Nucleophilic addition (Section 17 6) The charactenstic reac tion of an aldehyde or a ketone An atom possessing an un shared electron pair bonds to the carbon of the C=0 group and some other species (normally hydrogen) bonds to the oxygen... 

The location of the hydroxyl and aldehyde groups ortho to one another in saUcylaldehyde permits intramolecular hydrogen bonding, and this results in the lower melting point and boiling point and the higher acid dissociation constant observed relative to -hydroxybenzaldehyde. 

Many biological processes involve an "association" between two species in a step prior to some subsequent transformation. This association can take many forms. It can be a weak association of the attractive van der Waals type, or a stronger interaction such as a hydrogen bond. It can be an electrostatic attraction between a positively charged atom of one molecule and a negatively charged atom of another. Covalent bond formation between two species of complementary chemical reactivity represents an extreme kind of association. It often occurs in biological processes in which aldehydes or ketones react with amines via imine intermediates. 

The formyl C-H O hydrogen bond idea (Fig. 1.4) was first conceived for the catalyst 9 and its existence is supported by several X-ray studies of BX3 aldehyde... 

After 19 hours, no reaction between the zinc chelate 2 and benzaldehyde can be detected at 20 °C. However, 10 mol % of the zinc chelate effectively catalyzes theenantioselective addition of diethylzinc to aromatic aldehydes. The predominant formation of the S-configurated products, effected by this conformationally unambiguous catalyst, can be explained by a six-mem-bered cyclic transition state assembly17. The fact that the zinc chelate formed from ligand M is an equally effective catalyst clearly demonstrates that activation of the aldehyde moiety does not occur as a consequence of hydrogen bond formation between the ammonium proton of the pyrrolidine unit and the aldehydic oxygen. 

In the course of this study, the authors determined /Lvalues for dibenzyl, methyl phenyl, methyl p-nitrophenyl, di-p-tolyl, di-isopropyl and tetramethylene sulphoxides and for diethyl, dipropyl and dibutyl sulphites. The /Lscales are applied to the various reactions or the spectral measurements. The /Lscales have been divided into either family-dependent (FD) types, which means two or more compounds can share the same /Lscale, family-independent (FI) types. Consequently, a variety of /Lscales are now available for various families of the bases, including 29 aldehydes and ketones, 17 carboxylic amides and ureas, 14 carboxylic acids esters, 4 acyl halides, 5 nitriles, 10 ethers, 16 phosphine oxides, 12 sulphinyl compounds, 15 pyridines and pyrimidines, 16 sp3 hybridized amines and 10 alcohols. The enthalpies of formation of the hydrogen bond of 4-fluorophenol with both sulphoxides and phosphine oxides and related derivatives fit the empirical equation 18, where the standard deviation is y = 0.983. Several averaged scales are shown in Table 1588. 

Mechanisms of aldehyde oxidation are not firmly established, but there seem to be at least two main types—a free-radical mechanism and an ionic one. In the free-radical process, the aldehydic hydrogen is abstracted to leave an acyl radical, which obtains OH from the oxidizing agent. In the ionic process, the first step is addition of a species OZ to the carbonyl bond to give 16 in alkaline solution and 17 in acid or neutral solution. The aldehydic hydrogen of 16 or 17 is then lost as a proton to a base, while Z leaves with its electron pair. 

Proton acceptors within hydrogen bonds (aldehydes, ketones, ethers, esters, and nitroderivatives)... 

The enantioselectivity of the BINOL-Ti(IV)-catalyzed reactions can be interpreted in terms of several fundamental structural principles.42 The aldehyde is coordinated to Ti through an apical position and there is also a 0-HC=0 hydrogen bond involving the formyl group. The most sterically favored approach of the alkene toward the complexed aldehyde then leads to the observed product. Figure 10.2 shows a representation of the complexed aldehyde and the TS structure for the reaction. 

The enol form of malonaldehyde is favored over the tautomeric aldehyde due to the presence of an intramolecular hydrogen bond. It constitutes one of the smallest model systems... 

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