Aldehydes miscellaneous reactions

Miscellaneous Reactions.- The Schlosser-Wittig reaction of ylide (209) with aldehyde (208) and treatment of the intermediate 6-oxido ylide with perchloryl fluoride has been used to construct the 13-fluoro unit (210) in a total synthesis of (+)-13-fluoroprosta-... 

Amidocarbonylation aldehydes, 11, 512 enamides, 11, 514 overview, 11, 511-555 Amido complexes with bis-Cp titanium, 4, 579 Group 4, surface chemistry on oxides, 12, 515 Group 5, surface chemistry on oxides, 12, 524 with molybdenum mono-Cp, 5, 556 with mono-Cp titanium(IV) alkane elimination, 4, 446 amine elimination, 4, 442 characteristics, 4, 413 via dehalosilylation reactions, 4, 448 HCL elimination, 4, 446 metathesis reactions, 4, 438 miscellaneous reactions, 4, 448 properties, 4, 437... 

Miscellaneous Reactions. Many other reactions can be realized in the presence of BY. An interesting hydrolysis-reduction process transformed a derivative of secologanin into two different cyclic compounds, depending on the pH of the incubation. Here, a glucosidase activity afforded the intermediate aldehyde, which could be reduced or rearranged to different products (eq 17). 

Miscellaneous reactions. BINOL-phosphate ID has also found applications in a Pd-catalyzed allylation of aldehydes by l-benzhydrylamino-2-alkenes, and epoxidation of enals with t-BuOOH ... 

Miscellaneous reactions. The starting point of a practical route to P -amino acids is the proline-catalyzed Mannich reaction of aldehydes with a chiral iminium salt derived from A-benzyl-A-(a-phenethyl)amine. Condensation of aldehydes with A-Boc imines furnishes mainly i yn-adducts. "... 

Miscellaneous Reactions of Phosphines.- The basicities of a series of bidentate phosphines have been determined by a study of their enthalpies of protonation with trifluoromethanesulphonic acid in 1,2-dichloroethane. Ring-opening of sultones via nucleophilic attack by nitrogen occurs on treatment with tri-(2-pyridyl)phosphine, with the formation of the water-soluble phosphine systems (91). A novel aldehyde-olefination procedure is afforded by the reactions of aldehydes, diazomethanes, and tertiary phosphines in the presence of a catalytic amount of the powerful Lewis acid methyltrioxorhenium. Attempts to prepare carboxyphenylphosphines by the ring metallation of triphenylphosphine followed by... 

Miscellaneous Reactions.- A full report has appeared of the use of /er/-butyl 4-diethylphosphono-3-oxobutanthioates (232) in olefination reactions for the preparation of homologated 3-oxobutanthioates and hence of tetramic acid derivatives. The reaction of the phosphonate dianion (234) with the aldehyde (233) is a key step in a total synthesis of the tetramic acid antibiotic ( .)-tirandamycin B (235). Olefinations involving both ylides and phosphonates have been used to construct the triene (236) en route to the spirotetronate subunit of the aglycone of the antitumour antibiotic... 

Miscellaneous Reactions. Trimethylsilyldiazomethane converts acid- and base-sensitive maleic anhydride derivatives into the corresponding bis(methyl esters) (eq 70). Terminal silyl enol ethers are conveniently prepared from aldehydes by first treating the carbonyl compound with TMSC(Li)N2, followed sequentially by methanol and Rh2(OAc)4 (eq 71). The method works well with base-sensitive substrates and is superior to the attempted regioselective deprotonation/O-silylation of the corresponding methyl ketone. ... 

Miscellaneous Reactions. AICI3 has been used to catalyze the addition of allylsilanes to aldehydes and acid chlorides (eq 37). Cyclic ethers (pyrans and oxepins) have been prepared with hy-droxyalkenes (eq 38). The course of reactions between aldehydes and allylic Grignard reagents can be completely diverted to a-allylation by AICI3 (eq 39). The normal course of the reaction gives y-allylation products. 

Miscellaneous Reactions. A one-pot three components synthesis of a variety of primary 1-aminophosphonates was reported using Al(OTf)3 as a catalyst (eq 11). Relative to other Lewis acids, Al(OTf)3 generally offered the best reaction times and yields using various aldehydes. The reaction was also possible using various primary amines in the same conditions. ... 

Miscellaneous Reactions. MTO finds an interesting application in the peroxyacetalization of ketones, aldehydes, and acetals with H2O2 as the oxidant, 1,1-dihydroperoxides are obtained (eq 63). ... 

Miscellaneous Reactions. In the presence of aluminium chloride, allylsilanes and bis(trimethylsilyl) acetylene add to aldehydes to give good yields of the corresponding alcohols (Scheme 52). Pyrolysis of the diketo lactones (86) gives a)3-unsatur-ated ketones(87) and thus provides a useful alternative route to these compounds. ... 

Miscellaneous Curing Reactions. Other functional groups can react with the thiol terminal groups of the polysulfides to cross-link the polymer chains and build molecular weight. For example, aldehydes can form thioacetals and water. Organic and inorganic acids or esters can form thioesters. Active dienes such as diacrylates can add to the thiols (3). Examples of these have been mentioned in the Hterature, but none have achieved... 

Several other miscellaneous heterogeneously catalyzed reactions have been performed in the liquid phase. Hexane was successfully oxyfunctionalized with aqueous hydrogen peroxide by use of the zeolite TS-1 catalyst [50] and microwave-promoted acetalization of a number of aldehydes and ketones with ethylene glycol proceeded readily (2 min) in the presence both of heterogeneous (acidic alumina) and homogeneous (PTSA, Lewis acids) catalysts [51], Scheme 10.7. 

In miscellaneous oxidative processes of indoles, two methods for the preparation of 3-hydroxyindoles have been reported. The first approach involves initial Vilsmeier-Haack reaction of indole-2-carboxylates 176 to afford the corresponding 3-formyl analogs 177. Activation of the aldehyde with p-toluenesulfonic acid (PTSA) and Baeyer-Villiger oxidation with m-chloroperoxybenzoic acid (wi-CPBA) then affords high yields of the 3-hydroxy compounds 178 <00TL8217>... 

Miscellaneous Iminium Catalyzed Transformations The enantioselective construction of three-membered hetero- or carbocyclic ring systems is an important objective for practitioners of chemical synthesis in academic and industrial settings. To date, important advances have been made in the iminium activation realm, which enable asymmetric entry to a-formyl cyclopropanes and epoxides. In terms of cyclopropane synthesis, a new class of iminium catalyst has been introduced, providing the enantioselective stepwise [2 + 1] union of sulfonium ylides and ot,p-unsaturated aldehydes.As shown in Scheme 11.6a, the zwitterionic hydro-indoline-derived catalyst (19) enables both iminium geometry control and directed electrostatic activation of sulfonium ylides in proximity to the incipient iminium reaction partner. This combination of geometric and stereoelectronic effects has been proposed as being essential for enantio- and diastereocontrol in forming two of the three cyclopropyl bonds. 

Table 4.9 Miscellaneous aldehydes subjected to the Prato reaction with sarcosin.

Abstract This chapter covers one of the most important areas of Ru-catalysed oxidative chemistry. First, alkene oxidations are covered in which the double bond is not cleaved (3.1) epoxidation, cis-dihydroxylation, ketohydroxylation and miscellaneous non-cleavage reactions follow. The second section (3.2) concerns reactions in which C=C bond cleavage does occur (oxidation of alkenes to aldehydes, ketones or carboxylic acids), followed by a short survey of other alkene cleavage oxidations. Section 3.3 covers arene oxidations, and finally, in section 3.4, the corresponding topics for aUcyne oxidations are considered, most being cleavage reactions. 

Miscellaneous. There are several other reports on the application of this ligand to catalytic asymmetric reactions, although enantioselectivities are modest. Those reports include the Mukaiyama-Michael reaction, allylation of aldehydes, asymmetric Diels-Alder reaction, Mukaiyama-Aldol reaction of ketomalonate, aziridination reaction of a-imino esters, and asymmetric hetero-Diels-Alder reaction. ... 

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