Carbonyl selective conversion

Schemes 15 and 16 summarize the syntheses of intermediates that represent rings A and D of vitamin Bi2 by the Eschenmoser group. Treatment of lactam/lactone 51, the precursor to B-ring intermediate 8 (whose synthesis has already been described, see Scheme 8), with potassium cyanide in methanol induces cleavage of the y-lac-tone ring and furnishes intermediate 76 after esterification of the newly formed acetic acid chain with diazomethane. Intermediate 76 is produced as a mixture of diastereomers, epimeric at the newly formed stereocenter, in a yield exceeding 95%. Selective conversion of the lactam carbonyl in 76 into the corresponding thiolactam...

Although neither of the two carbonyl groups in 18 is immune to the action of Lawesson s reagent,11 it is possible to bring about the selective conversion of the more Lewis-basic lactam carbonyl to the corresponding thiocarbonyl. Thus, treatment of 18 with Lawesson s reagent results in the formation of thiolactam 19 in 85% overall yield from 13. 

Enones and enoates undergo 1,2-reduction [115, 191]. Lipshutz et al. reported the effective protection of carbonyl functions by the triisopropylsilyl acyl silane group (TIPS), which allowed the selective conversion of alkenes or alkynes to the corresponding zirconocene complexes [24]. The aldehyde could subsequently be regenerated by desilylation with TBAF [186]. 

Selective Conversion of Carbonyl Ligands on (T 5-C-,H.-,)Fe(COy to G> Organic Compounds... 

In a slightly less convenient procedure, but one which has general versatility, carbonylation of aryl (or vinyl) palladium compounds produces aryl, heteroaryl, and vinyl carboxylic acids. As with the other procedures, immediate upon its formation, the carboxylate anion migrates to the aqueous phase. Consequently, haloaromatic acids can be obtained from dihaloarenes, without further reaction of the second halogen atom, e.g. 1,4-dibromobenzene has been carbonylated (90% conversion) to yield 4-bromobenzoic acid with a selectivity for the monocarbonylation product of 95%. Additionally, the process is economically attractive, as the organic phase containing the catalyst can be cycled with virtually no loss of activity and ca. 4000 moles of acid can be produced for each mole of the palladium complex used [4],... 

Marcantoni E, Nobili F, Bartoli G, Bosco M, Sambri L (1997) Cerium(III) chloride, a novel reagent for nonaqueous selective conversion of dioxolanes to carbonyl compounds. J Org Chem 62 4183 1184... 

Halcon has developed a new non-noble metal catalyst for methanol reductive carbonylation (32). It is formed under more moderate conditions (1200 psi, 120 C) and permits a selective reaction at only 1200-1800 psi of reaction pressure. Under these conditions, the catalyst s activity is comparable with noble metal catalyzed carbonylations. The conversion rate is 1.5-3.0 mol/l.hr. and acetaldehyde selectivity is 85%. In concentrated solutions, a considerable portion of product acetaldehyde (20-40%) is converted to its acetal. The acetal can be readily hydrolyzed back to acetaldehyde at 100-150 without catalyst (33). Acetal formation is actually beneficial through prevention of undesirable acetaldehyde condensation reactions. 

Asymmetric hydrogenation of simple 2-cyclohexenone is still difficult. A catalyst system prepared in situ from [Ir(OCH3)(cod)]2 and DIOP shows carbonyl-selectivity as high as 95% at 65% conversion, but with a poor enantioselectivity (Scheme 1.69) [274],... 

Trichloro(methyl)silane-Sodium iodide, 11, 553-554. This in situ equivalent of io-dotrimethylsilane is also effective for cleavage of esters and lactones, selective conversion of tertiary and benzylic aleohols into iodides, dehalogenation of a-halo ketones, deoxygenation of sulfoxides, and conversion of dimethyl acetals to carbonyl compounds. ... 

In the reductive dimerization of methyl cinnamate to a cyclopentanone [Eq. (5)], similar yields are found at the cathode [42] and with metals (sodium, THE, and TBAI, —78°C) [40]. Because of the potential selective conversion at the electrode, halides can be reduced at the cathode to carbanions in the presence of carbonyl compounds, which are reduced at more cathodic potentials. This way labile carbanions can be obtained and reacted under conditions in which the same species generated by a metalorganic route would decompose. Eor example, trichlorobromoalkane can be cathodically converted in the presence of aldehydes to a dichloromethyl anion 0°C [route a, Eq. (6)] and be trapped to form a dichlorotetrahydrofuran, but for the metallorganic route [route b, Eq. (6)] a reaction temperature of — 110°C is necessary [43]. 

Hayakawa and co-workers have intensively developed HPLC techniques with on-line reduction of NPAC to aminoPAC (APAC) and chemiluminescence detection of APAC for trace analysis of NPAC, particularly of nitropyrenes. In this study, we examined the HPLC method for the analysis of novel NPAC, 3-NBA and 2-NTP in airborne particles including the interference of coexisting NPAC in the sample in separation and the efficiency of the on-line reduction to selective conversion of 3-nitrobenzanthrone, which has one carbonyl group, to detectable 3-aminobenzanthrone in the HPLC system. 

Carbonyl-selective asymmetric hydrogenation of simple 2-cyclohexenone is still difficult. The optical yield obtained with [Ir(OCH3)(cod)]2-DIOP is only 25%, while the carbonyl-selectivity is 95% at 65% conversion (Scheme 23) [80]. Hydrogenation of 2,4,4-trimethyl-2-cyclohexenone with a Ru(II)-TolBINAP-4-KOH catalyst system under 8 atm of hydrogen at 0 °C gives 2,4,4-trimethyl-2-cy-clohexenol quantitatively in 96% ee [81, 82]. Notably, the combination of (R)-TolBINAP and (S,S)-4 matched well to give the S alcohol with a high ee. The chiral allylic alcohol is the key intermediate in the synthesis of carotenoid-derived odorants and other bioactive compounds [83]. 

Needless to say, solid acid and base catalysts play a key role in the transformation of biomass-derived materials to value-added compounds such as carbonyl compounds [21-33]. For example, lactic acid could be obtained from cellulose using tungstated alumina as a Lewis add catalyst [137], and from glucose using HT as a solid base catalyst [138]. In this parL selective conversions of biomass-sourced materials using solid acid and base catalysts are surveyed alongside mechanistic considerations. 

Carbonylation of Olefins. Two catalysts 1% Pd/0.8 CaNaY, and 1% Pd/HMOR were tested in propylene carbonylation (14). Both Pd-containing zeolite catalysts exhibit high activity and selectivity, conversion to butyric acids being 97-99% (Table 6). The change of the nature of the zeolite does not affect the yield and composition of the reaction products. However, Pd/zeolite catalysts are destroyed during the cause of the experiments by both the acid used as the solvent and the acid formed in the reaction. According to x-ray analysis 100% destruction of zeolite structure was observed after the end of experiment. 

A convenient and clean water-mediated synthesis of a series of 4-amino-2-ar-yl-1,2-dihydro pyrimido[l,2-a]benzimidazoles has been reported using alternative nonconventional energy sources [37]. The products were obtained in shorter times with excellent yields (78-89 %) from the multicomponent reaction of 2-ami-nobenzimidazole, malononitrile/ethylcyanoacetate, and carbonyl compounds (Scheme 8.26). The procedure does not involve the use of aity additional reagent/ catalyst, produces no waste, and represents a green synthetic protocol with high atom economy. The combination of microwave irradiation, ultrasonic irradiation, and aqueous-mediated conditions using multicomponent reactions leads to enhanced reaction rates, higher yields of pure products, easier workup, and sometimes selective conversions. Consequently, this protocol should be welcome in these environmentally aware days. 

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