Carbonyl functions, transformation

The target compound is searched for a rctron. A retron is the structural subunit required to be present in the target in order to apply a transform. In Figure 10,3-30 the rctron of a Michael addition is a sequence of five carbon atoms with two carbonyl functions in the 1,5-position. For a Michael addition transform to be applied, it has to be present,... 

The lithium etiolate of acetaldehyde DMH has recently been utilized in the opening reaction of the ot-epoxide obtained by DM DO oxidation ofenol ether 142, to provide hemiacetal 143 after mild oxidative acid hydrolysis. The protected carbonyl functionality was subsequently used for the introduction of the trans enyne chain through a Wittig olefmation reaction to provide alcohol 144, which was then transformed into (+)-laurenyne (Scheme 8.37) [71]. 

Photochemical changes in both II and the acetoxy derivative have been monitored in fluid solution and incorporated in a polymer film. Fig. 5 shows the spectral changes accompanying photochemical transformation of the acetoxy derivative. Then changes may be interpreted in terms of scheme 3, which proposes a photochemical 1,3 acyl shift to form "in situ" an ultraviolet stabilizer chromophore which also has a carbonyl functionality. 

Diphenylcyclopropene thione (156) was prepared11S-12°) from 3,3-dichloro-1,2-diphenyl cyclopropene (154) by reaction with thioacetic acid, since transformation of the carbonyl function of diphenyl cyclopropenone with P4S10121 was complicated by ring expansion to the trithione 155122 In a useful recent thioketone synthesis123) 156 was obtained directly from diphenyl cyclopropenone in a quantitative yield by simultaneous treatment with HC1 and H2S. 

Hydrogenation of the carbonyl function is an important synthetic transformation and can be catalyzed by complexes of several transition metals including -among others- Co, Rh, Ru, Ir, and Os. In aqueous organometallic catalysis the first examples were given by the hydrogenation of water-soluble 2-oxo-carboxylic acids, 1,3-dihydroxyacetone and fmctose [47-54], later the same substrates were also used for testing new catalysts [29]. 

From these products the carbonyl function can be liberated in acidic media or in the presence of fluoride ions. This methodology provides an attractive route to transform a CH2—X group (X = PhS, MeS, CN) into the corresponding CHO, allowing the preparation of aldehydes, e.g. formyltrimethylsilane, which was generated and trapped in situ using a Wittig reaction (Scheme 7)45. 

A new method for the synthesis of 2-substituted, as well as 2,4- and 2,5-disubstituted, cyclopentanones in 53-93% yield has been reported.81 For example, the Lewis acid catalyzed transformation of l-propanoyl-l-(4-tolylsulfanyl)cyclobutane gave 2-ethyl-2-(4-tolylsulf-anyl)cyclopentanone (1) in 93 % yield. The formation of the cyclopentanone is best explained by a mechanism which involves initial coordination of aluminum trichloride to the carbonyl oxygen, followed by ring expansion to form the sulfur-stabilized carbocation. Finally, migration of the ethyl group to the carbocation center regenerates concomitantly the carbonyl function.81... 

Pyrroles and fiirans were prepared by the intramolecular carbon-carbon bond formation between pendant acetylene and nitrile or carbonyl functions. The process, running in acetic acid, starts by the fraw-acetoxypalladation of the acetylene moiety, which initiates a series of further transformations. The nature of the ring formed is determined by heteroatom bridging the two reactive units. The propargylamine derivative in 3.88., for example gave a pyrrole ring.112... 

The reactions catalyzed by Lewis acids are conducted for 10-20 hours at — 20 C to give hypochlorites in almost quantitative yield.82 Chlorine monofluoride activated by hydrogen fluoride to enhance its electrophilicity transforms the carbonyl function in esters of carboxylic acids to a difluoromethyl group. The reactions are carried out by passing 2molar equivalents of chlorine monofluoride gas through a solution of the ester in an equal volume of hydrogen fluoride at - 70 to - 30°C.83... 

The role of specific interactions in the plasticization of PVC has been proposed from work on specific interactions of esters in solvents (eg, hydrogenated chlorocarbons) (13), work on blends of polyesters with PVC (14—19), and work on plasticized PVC itself (20—23). Modes of interaction between the carbonyl functionality of the plasticizer ester or polyester were proposed, mostly on the basis of results from Fourier transform infrared spectroscopy (ftir). Shifts in the absorption frequency of the carbonyl group of the plasticizer ester to lower wave number, indicative of a reduction in polarity (ie, some interaction between this functionality and the polymer) have been reported (20—22). Work performed with dibutyl phthalate (22) suggests an optimum concentration at which such interactions are maximized. Spectral shifts are in the range 3—8 cm-1. Similar shifts have also been reported in blends of PVC with polyesters (14—20), again showing a concentration dependence of the shift to lower wave number of the ester carbonyl absorption frequency. 

It is worth considering a bit the proiecting-group strategy that has here been employed. The double bond introduced at the beginning of the synthesis (3 —> 4 is not activated in the form of an aldehyde equivalent until the transformation of 7 into 8 This is an example of the place-holder concept 6 In this way alkenes or protected alcohols - which are simpler and can be protected in various ways - are introduced in the course of a synthesis as equivalents for sensitive carbonyl functions. 

Formation of Oximes - Carbonyl functional groups can be transformed into an oxime derivative by alcoholic hydroxylamine chlorohydrate and monitored by the liberation of HC1. 

In order to transform the spirocyclic enone 445 to ( )-elwesine (439) and ( )-epielwesine (449), it was treated with boron trifluoride and dimethylsulfide to cleave the Al-carbobenzyloxy protecting group, and cyclization of the resulting amino enone spontaneously ensued to produce ( )-dihydrooxocrinine (447). Reduction of carbonyl function of 447 with sodium borohydride afforded ( )-3-epielwesine (449), which was converted to ( )-elwesine (439) by inversion of the hydroxyl function at C-3 via a Mitsunobu protocol using diethyl azodicarboxylate, triphenylphosphine, and formic acid. Attempted reduction of 447 directly to 439 by a Meerwein-Ponndorf-Verley reduction or with bulky hydride reagents gave only mixtures of 449 and 439 that were difficult to separate. 

A procedure for the transformation of (+)-tazettine (397) to (+)-pretazettine (395) has been developed (212). The reaction of 397 with LiAlH4 provided a mixture of the diols 536 and 537 in an approximately 9 2 ratio. Thus, it is again apparent that the preferred stereochemical pathway for the delivery of hydride to the neopentyl carbonyl function is from the endo face of the cis-3a-arylhydroin-dole whenever the angular aryl group possesses an ortho substituent. Oxidation of 537 with manganese dioxide gave a mixture (approximately 3 2 1) of (+)-pretazettine (395), (+)-3-epimacronine (400), and (+)-tazettine (397). In a sim-... 

Kinetic resolution of chiral, racemic anhydrides In this process the racemic mixture of a chiral anhydride is exposed to the alcohol nucleophile in the presence of a chiral catalyst such as A (Scheme 13.2, middle). Under these conditions, one substrate enantiomer is converted to a mono-ester whereas the other remains unchanged. Application of catalyst B (usually the enantiomer or a pseudo-enantiomer of A) results in transformation/non-transformation of the enantiomeric starting anhydride ). As usual for kinetic resolution, substrate conversion/product yield(s) are intrinsically limited to a maximum of 50%. For normal anhydrides (X = CR2), both carbonyl groups can engage in ester formation, and the product formulas in Scheme 13.1 are drawn arbitrarily. This section also covers the catalytic asymmetric alcoholysis of a-hydroxy acid O-carboxy anhydrides (X = O) and of a-amino acid N-carboxy anhydrides (X = NR). In these reactions the electrophilicity of the carbonyl groups flanking X is reduced and regioselective attack of the alcohol nucleophile on the other carbonyl function results. 

A variety of functional transformations occurring far from the SMA framework have been described. Acylation of a silyl ether, sodium borohydride or LAH reduction of an ester into a carbinol, oxidation of a carbinol into an aldehyde or a ketone, and the addition of Grignard reagents to a carbonyl are some examples.95,168,255... 

The latter example (reaction 36) already indicates that the Yang cydization can also be used to synthesize four-membered heterocycles. After light absorption, the a,(3-unsaturated carbonyl compound 84 undergoes intramolecular hydrogen abstraction at the a-position of the carbonyl moiety (reaction 37), leading to the 1,4-biradical intermediate XXX [87]. A radical combination then efficiently yields the spirocyclic P-lactam derivative 85, and only one stereoisomer is formed in this case. In this transformation, the a,P-unsaturated carbonyl function can be considered as being vinylogous to a simple ketone. 

Metal complexes enable one to employ molecules that are thermally unreactive toward cycloadditions by taking advantage of their ability to be activated through complexation. Most of the molecules activated by transition-metal complexes involve C-C unsaturated bonds such as alkynes, alkenes, 1,3-dienes, allenes, and cyclopropanes. In contrast, carbonyl functionalities such as aldehydes, ketones, esters, and imines seldom participate in transition-metal-catalyzed carbonylative cycloaddition reactions. Recently, such a transformation was reported via the use of ruthenium complexes. 

Finally, this catalyst system was applied to the chemoselective, diastereose-lective, and enantioselective reduction of racemic 2-alkyl-l,3-diketones [57]. Scheme 11 shows examples of this transformation catalyzed by (R,R)-15. To minimize the effects of uncatalyzed reduction, four portions of 0.1 equivalents of modified borohydride with THFA and ethanol (i.e., total 0.4 equiv) were successively added to the substrate solution at -20°C. The selectivity of the carbonyl group at the benzylic position over the simple aliphatic carbonyl function (in... 

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