Miscellaneous reactions reaction with aldehydes

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... 

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-... 

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

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. 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. Double lithiations of the parent compounds give the dianions (25) and (26), both of which react with electrophiles preferentially at the benzyl positions. Addition of RLi to the carbonyl group of compound (27), followed by reduction of the initial product, gives access to 4-alkyl-2,6-di-t-butylanilines. Low-temperature reactions between aldehydes and RLi in the presence of asymmetric auxiliaries such as (28) give secondary alcohols with up to 40% enantiomeric... 

Miscellaneous Fused Selenophens.—Selenolo[2,3-6]thiophen (691) has been prepared by metalation of thiophen>3-aldehyde diethyl acetal with butyl-lithium followed by reaction with selenium and methyl chloroacetoacetate. The intermediate (692) was, without isolation, hydrolysed and ring-closed to (693), which upon decarboxylation gave (691). Another isomeric... 

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. 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). ... 

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 Applications.— The Wittig reaction of ( ) 6,10-dimethyl 5,9-undecadien-2-ylidenetriphenylphosphorane with ethyl rra/ (2-carboxaldehyde)-cyclopropanecarboxylate yields a 1 1 mixture of ( )- and (Z)-alkenes. The former isomer was converted into an analogue (161) of a proposed intermediate in squalene biosynthesis. (10 ,ll/ )-(+)-Squalene-10,ll-epoxide (164), identical to a constituent of the red algae Laurencia okamuri, was isolated from the isomeric mixture produced from a Wittig reaction of the ylide (162) with the aldehyde (163). ... 

Miscellaneous.—Several useful lithium-based synthetic procedures have been reported this year which involve the preparation or further functionalization of carbonyl compounds. For example aldehydes can be prepared by reaction of an organolithium, RLi, with the formylpiperidine (50). Unsymmetrically... 

Miscellaneous. An asymmetric Henry reaction involving combination of an aldehyde with a silyl nitronate, catalyzed by Cu(OTf)2 in the presence of TBAT and a chiral BOX ligand, gives the nitroaldol products in moderate yield and stereoselectivity. TBAT is effective in triggering desilylation of certain functionalized silyloximes, resulting in concomitant cyclization and nitrone formation (eq 9) ... 

Biochemical and Miscellaneous.—3-Methyl-2-benzothiazolone hydrazone is incorporated quantitatively into the anticodon loop of t-RNA" from yeast. Reaction occurs by Schiff s base formation with the ribose aldehyde group remaining after excision of the base Y from the nucleotide. The reaction provides a method of chemically modifying the natural polymer, with retention of its biochemical activity." ... 

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