Aldehydes reactions, summary

Scheme 1. Am1de/Blocked Aldehyde Reaction Summary...

As previously discussed two modes of addition (endo and exo) are possible for the orientation of the diene with respect to the aldehyde. In addition to these orientations are preferences for a particular diastereofacial selectivity (CF, ACF) for reactions with chiral aldehydes. A summary of these relationships and how the diastereofacial selectivity can be controlled by use of different Lewis acid catalysts is given in Table IS and Scheme 19. 

Summary of Reactions Discussed in Earlier Chapters That Yield Aldehydes and Ketones... 

Summary of Reactions of Aldehydes and Ketones Discussed in Earlier Chapters... 

In summary, the Bucherer-Bergs reaction converts aldehydes or ketones to the corresponding hydantoins. It is often carried out by treating the carbonyl compounds with potassium cyanide and ammonium carbonate in 50% aqueous ethanol. The resulting hydantoins, often of pharmacological importance, may also serve as the intermediates for amino acid synthesis. 

The enantioselectivities of the reactions of representative achiral aldehydes and chiral allylboron reagents arc compared in Table 4. A comparison of the enantioselectivities of the (Z )-2-butenyl reagents appears in Table 5, while Table 6 provides a similar summary of the reactions of the (Z)-2-butenyl and 3-methoxy-2-propcnyl reagents. A 3-diphenylamino-2-propenyl reagent was recently reported102. 

Summary of the Relationship between Diastereoselectivity and the Transition Structure. In this section we considered simple diastereoselection in aldol reactions of ketone enolates. Numerous observations on the reactions of enolates of ketones and related compounds are consistent with the general concept of a chairlike TS.35 These reactions show a consistent E - anti Z - syn relationship. Noncyclic TSs have more variable diastereoselectivity. The prediction or interpretation of the specific ratio of syn and anti product from any given reaction requires assessment of several variables (1) What is the stereochemical composition of the enolate (2) Does the Lewis acid promote tight coordination with both the carbonyl and enolate oxygen atoms and thereby favor a cyclic TS (3) Does the TS have a chairlike conformation (4) Are there additional Lewis base coordination sites in either reactant that can lead to reaction through a chelated TS Another factor comes into play if either the aldehyde or the enolate, or both, are chiral. In that case, facial selectivity becomes an issue and this is considered in Section 2.1.5. 

In summary, gas-phase reactions between aldehydes and NOj occur readily and with strong exothermicity. The rate of reaction is largely dependent on the alde-hyde/N02 mixture ratio, and is increased with increasing NO2 concentration for aldehyde-rich mixtures. On the other hand, no appreciable gas-phase reactions involving NO are likely to occur below 1200 K. The overall chemical reaction involving NO appears to be third order, which impUes that it is sensitive to pressure. The reactions discussed above are important in understanding the gas-phase reaction mechanisms of nitropolymer propellants. 

In summary, the differences between Br0nsted-acid catalysis and hydrogen-bond catalysis were discussed. Because there is a gradual transition from hydro-gen-bond catalysis to Bronsted-acid catalysis, it is not always easy to differentiate the two modes of catalysis. However, the combination of a stronger acid and an imine will be a Bronsted-acid-catalyzed reachon, while the combination of a neutral acid and an aldehyde will be a hydrogen-bond-catalyzed reaction. 

Five- and Six-Membered Ring Heterocycles with One, Two, or Three Sulfur Atoms. A summary of the various sulfur heterocycles formed from aldehydes in the presence of hydrogen sulfide and the corresponding analytical data are presented in Table I. Examples of aldehydes used in this reaction include propionaldehyde, butyraldehyde and caproaldehyde. 

A chapter written in 1996 covers hydroformylation catalyzed by organometallic complexes in detail,219 whereas a review written 5 years later gives a summary of the advances on hydroformylation with respect to synthetic applications.220 A selection of papers in a special journal issue has been devoted to carbonylation reactions.221 A major area of the research has been the development of fluorous biphasic catalysis and the design of new catalysts for aqueous/organic biphasic catalysis to achieve high activity and regioselectivity of linear or branched aldehyde formation. 

Free amino acids are further catabolized into several volatile flavor compounds. However, the pathways involved are not fully known. A detailed summary of the various studies on the role of the catabolism of amino acids in cheese flavor development was published by Curtin and McSweeney (2004). Two major pathways have been suggested (1) aminotransferase or lyase activity and (2) deamination or decarboxylation. Aminotransferase activity results in the formation of a-ketoacids and glutamic acid. The a-ketoacids are further degraded to flavor compounds such as hydroxy acids, aldehydes, and carboxylic acids. a-Ketoacids from methionine, branched-chain amino acids (leucine, isoleucine, and valine), or aromatic amino acids (phenylalanine, tyrosine, and tryptophan) serve as the precursors to volatile flavor compounds (Yvon and Rijnen, 2001). Volatile sulfur compounds are primarily formed from methionine. Methanethiol, which at low concentrations, contributes to the characteristic flavor of Cheddar cheese, is formed from the catabolism of methionine (Curtin and McSweeney, 2004 Weimer et al., 1999). Furthermore, bacterial lyases also metabolize methionine to a-ketobutyrate, methanethiol, and ammonia (Tanaka et al., 1985). On catabolism by aminotransferase, aromatic amino acids yield volatile flavor compounds such as benzalde-hyde, phenylacetate, phenylethanol, phenyllactate, etc. Deamination reactions also result in a-ketoacids and ammonia, which add to the flavor of... 

In summary, Figure 9.15 presents a method for the mild esterification of carboxylic acids. For example, it allows for the chemoselective esterification I —> J. Only under these reaction conditions does this sensitive substrate (I) not experience an addition of methanol to the C=C double bond, a C=C double bond migration or an acetalization of the aldehyde function. 

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