Unsaturated compounds conjugated carbonyls

The unsaturated molecule Y may be carbon monoxide, an olefin, a conjugated diene, an acetylene, a carbonyl compound, various unsaturated carbon-nitrogen compounds, or probably any of several other unsaturated materials. The reactive part of the covalent metal compound is usually a metal-hydrogen, metal-carbon, metal-oxygen, metal-halogen, metal-nitrogen, or metal-metal group. This reaction... 

Other Rh catalysts were also employed for hydrosilation of a,p-unsaturated carbonyl compounds and unsaturated nitriles. Thus, Rh(acac)2 and a tetrakis( jL-acetato)dirhodium cluster were used as catalysts in the hydrosilation of a,P-unsaturated aldehydes. These reactions, however, are not chemoselective, as alkynes, conjugated dienes and alkenes are also hydrosilylated, and allylic heterosubstituents are reduc-tively cleaved. 

Sodium borohydride, NaBH4, does not reduce carbon-carbon double bonds, not even those conjugated with carbonyl groups, and is thus useful for the reduction of such unsaturated carbonyl compounds to unsaturated alcohols. 

The anion of an aldehyde dithioacetal 5-oxide is well known to add to a,3-unsaturated carbonyl compounds. " Conjugate addition of formaldehyde di-p-tolyl dithioacetal 5-oxide (114) to open-chain and cyclic enones is achieved by using HMPA as a polar cosolvent in THF (-78 C)." The lithio derivative of (5)-(114) was found to add to 2-cyclopentenone with asymmetric induction. Transformation of the dithioacetal part into a formyl group gives 3-formylcyclopentanone in 39% enantiomeric excess (equation 28)." Interestingly, highly asymmetric induction is observed in the conjugate addition of the... 

Carbonyl group reduction. With LiBH4 as catalyst the reduction prevails over hydroboration of unsaturated carbonyl compounds. Conjugated alkenones give allylic alcohols. 

In this work we have shown that Ziegler type cobalt catalysts are rather selective for the hydrogenation of unsaturated carbonyl compounds into unsaturated alcohols. Nevertheless the selectivity was more important with cinnamaldehyde than with other aldehydes, which showed the eflfect of the aromatic cycle on the stabilization and the adsorption of the conjugated double bond. 

Trialkylstannyl-lithium reacts with secondary alkyl halides (substitution) and with a/S-unsaturated carbonyl compounds (conjugate addition) to give alkyl tin derivatives which may be oxidized with chromic anhydride in pyridine to give a saturated ketone. Applying the procedure to a cycloalkenone, an efficient dialkyl-ative enone transposition can be realized (Scheme 68). ... 

The Friedel-Crafts metathesis catalytic systems are versatile systems capable of resulting a great variety of reactions. The new routes for polymerization of cc,p-unsaturated carbonyl compounds, conjugated dicarbonyl compounds and their copolymerization with strained cycloolefins are among them. The syntheses are very... 

In contrast, when (PhC2H)Co2(CO)6 was heated with a, -unsaturated carbonyl compounds, conjugated dienes were obtained in moderate yield [Eq. (104)] (Khand and Pauson, 1974). Crotonaldehyde gave the corre-... 

Addition of dihydrosilane to a, /J-unsaturated carbonyl compounds such as citral (49), followed by hydrolysis, affords saturated citroneJlal (50) directly. The reaction is used for the selective reduction of conjugated double bonds[45,46]. In addition to Pd catalyst, the use of a catalytic amount of... 

CONJUGATE ADDITION OF ORGANOCOPPER REAGENTS TO a,p-UNSATURATED CARBONYL COMPOUNDS... 

P carbon atom of an a 3 unsatu rated carbonyl compound is elec trophilic nucleophiles especially weakly basic ones yield the prod ucts of conjugate addition to a 3 unsaturated aldehydes and ketones... 

Stabilized anions exhibit a pronounced tendency to undergo conjugate addition to a p unsaturated carbonyl compounds This reaction called the Michael reaction has been described for anions derived from p diketones m Section 18 13 The enolates of ethyl acetoacetate and diethyl malonate also undergo Michael addition to the p carbon atom of a p unsaturated aldehydes ketones and esters For example... 

Ammonia and amines undergo conjugate addition to a 3 unsaturated carbonyl compounds (Section 18 12) On the basis of this information predict the pnncipal organic product of each of the following reactions... 

Acrolein (H2C=CHCH=0) undergoes conjugate addition with sodium azide in aqueous solution to give N3CH2CH2CH=0 Propanal is not an a 3 unsaturated carbonyl compound and cannot undergo conjugate addition... 

Mesityl Oxide. Mesityl oxide (MSO) (4-metliyl-3-penten-2-one) is an oily colorless liquid with an unpleasant odor. It exhibits the versatiUty and unusual reactivity associated with conjugated a,P unsaturated carbonyl compounds (172). On standing ia air, mesityl oxide slowly forms bis(3,5,5-trimethyl-l,2-dioxolanyl)-3-peroxide (173). 

Methacryhc acid and its ester derivatives are Ctfjy -unsaturated carbonyl compounds and exhibit the reactivity typical of this class of compounds, ie, Michael and Michael-type conjugate addition reactions and a variety of cycloaddition and related reactions. Although less reactive than the corresponding acrylates as the result of the electron-donating effect and the steric hindrance of the a-methyl group, methacrylates readily undergo a wide variety of reactions and are valuable intermediates in many synthetic procedures. 

These reversible reactions are cataly2ed by bases or acids, such as 2iac chloride and aluminum isopropoxide, or by anion-exchange resias. Ultrasonic vibrations improve the reaction rate and yield. Reaction of aromatic aldehydes or ketones with nitroparaffins yields either the nitro alcohol or the nitro olefin, depending on the catalyst. Conjugated unsaturated aldehydes or ketones and nitroparaffins (Michael addition) yield nitro-substituted carbonyl compounds rather than nitro alcohols. Condensation with keto esters gives the substituted nitro alcohols (37) keto aldehydes react preferentially at the aldehyde function. 

In the presence of suitable a,/5-unsaturated carbonyl compounds (3) the nucleophilic methylide (2) undergoes conjugate addition followed by expulsion of dimethyl sulfoxide to give cyclopropanes (5). 

Conjugate addition (Sections 10.10 and 18.12) Addition reaction in which the reagent adds to the termini of the conjugated system with migration of the double bond synonymous with 1,4 addition. The most common examples include conjugate addition to 1,3-dienes and to a,(3-unsaturated carbonyl compounds. 

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