O,0-Unsaturated carbonyl compounds

This reaction has been modified to occur between jS-alkoxyl o, )0-unsaturated carbonyl compounds and hydrazines. ... 

It is believed that the coordination of o, )0-unsaturated carbonyl compounds to Lewis acid facilitates this reaction, as illustrated by the tentative mechanism given here. 

Strategy The overall result of an enamine reaction is the Michael addition of a ketone as donor to an o, /3-unsaturated carbonyl compound as acceptor, yielding a 1,5-djcarbonyl product. The C-C bond made in the Michael addition step is the one between the carbon of the ketone donor and the 0 carbon of the unsaturated acceptor. In the present instance ... 

A delocalized 0-stannyl radical anion can also be generated from the reaction of an a,/ -unsaturated ketone or aldehyde with tributyltin hydride and radical initiator AIBN [3, 4, 5a, 5b]. Thus, a,/ -unsaturated carbonyl compound 4 (R or R = H or alkyl), can be reacted with wBu SnH under standard free-radical conditions to give allylic O-stannyl ketyl species (5 6), shown in Scheme 2. After hydrogen atom transfer to the -position of 6, a synthetically useful tin(IV) enolate is produced [5b, 5d, 5g. Allylic 0-stannyl ketyls have both one- (radical) and two-electron (anionic) sites for reactivity. These reactions can proceed in a sequential manner - a rapidly-evolving methodology in organic synthesis [2, 5, 8j. If the one-electron reactivity in 6 is used with a radicophile, then the tin enolate or two-electron reactivity can be used in reactions with suitable electrophiles (E ). Note that the carbonyl species. 

Besides the aldol reaction to form y0-hydroxyketone, 1,3-Dipolar Cycloaddition can also form similar molecules. In addition to the Mukaiyama Aldol Reaction, the following are also similar or closely related to the aldol reaction the Claisen-Schmidt Condensation (the aldol reaction between benzaldehyde and an aliphatic aldehyde or ketone in the presence of relatively strong bases to form an o, )0-unsaturated aldehyde or ketone), the Henry Reaction (base-catalyzed addition of nitroalkane to aldehydes or ketones), the Ivanov Reaction (the addition of enediolates or aryl acetic acid to electrophiles, especially carbonyl compounds), the Knoevenagel Reaction (the condensation of aldehydes or ketones with acidic methylene compounds in the presence of amine or ammonia), the Reformatsky Reaction (the condensation of aldehydes or ketones with organozinc derivatives of of-halo-esters), and the Robinson Annulation Reaction (the condensation of ketone cyclohexanone with methyl vinyl ketone or its equivalent to form bicyclic compounds). 

The a,(3-unsaturated carbonyl compound has three resonance structures, two of which place a single bond between the C and O atoms. This means that the C-0 bond has partial single bond character, making it weaker than a regular C=0 bond, and moving the absorption to lower wavenumber. 

Alkenylation of a, -unsaturated carbonyl compounds (513) (X = CH2, O, NBoc n = 0, 1) with alkenyltrifluoroborates RBF3K, catalysed by chiral [Rh(OH)(diene)]2 complexes, has been developed as an enantioselective method for obtaining the corresponding Michael adducts with <99% ee. 1... 

Two different alkenes can be brought to reaction to give a [2 -I- 2] cycloaddition product. If one of the reactants is an o, /3-unsaturated ketone 11, this will be easier to bring to an excited state than an ordinary alkene or an enol ether e.g. 12. Consequently the excited carbonyl compound reacts with the ground state enol ether. By a competing reaction pathway, the Patemo-Buchi reaction of the 0, /3-unsaturated ketone may lead to formation of an oxetane, which however shall not be taken into account here ... 

The photochemical oxidation reactions of unsaturated organic molecules lead to the formation of peroxides which are characterized by the weak bond O-O. In terms of bond energies this is one of the weakest covalent bonds weak enough to be split in thermal processes. When a cyclic peroxide dissociates into carbonyl compounds, one of these may be formed in an electronically excited state (Figure 4.83). The energy difference results from the loss of the weak 0-0 bond and the formation of two C=0 tt bonds over 60kcalmol-1 is then available as free energy. There are also reasons of... 

The presence of two electrophilic reaction centers in the molecule of o -unsaturated carbonyls is responsible for their ability to participate in the synthesis of heterocycles. Such compounds can react as ambident electrophiles owing to delocalization of electron density in a C=C-C=0 system. The addition of nucleophiles to these molecules can proceed in one of two main directions—via attack of the carbonyl group (1,2-addition) or involving the / -carbon (1,4-addition). 

The Claiscn rearrangement of allyl vinyl ethers is usually an irreversible reaction due to the energetic benefit of forming aC-O double bond. However, in strained bicyclic systems the retro-Claisen rearrangement (3-oxa-Cope rearrangement) of y,<5-unsaturated aldehydes has been observed32. Sometimes equilibrium mixtures of vinyl ether and carbonyl compound were found. For example, the ratio of the valence tautomers, bicyclo[3.1.0]hex-2-ene-6-cWo-methanal to 2-oxabicyclo[3.2.l]octa-3,6-diene, is approximately 7 333. Nevertheless this reaction was used in the preparation of a key intermediate in a prostacyclin synthesis34. 

Atmospheric chemistry demands have given a nuuked stimulus to studies of reactions of 0 atoms and OH- radicals with atmospheric substrates at about room temperature and below. Reactions of O atoms with alkenes and aromatics are important in photochemical smog formation and control. Rate constants, and in many cases Arrhenius parameters, are available for a variety of -O atom reactions with alkenes, alkynes, aromatics, unsaturated aldehydes, alkanes, - and carbonyl compounds. In general, the rate constants refer to the ovoall process ... 

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