Benzyl thioether

Na, NH3, 10 min. Sodium in boiling butyl alcohol or boiling ethyl alcohol can be used if the benzyl thioether is insoluble in ammonia. 

Hg(OAc)2, H2O, 80% AcOH, HSCH2CH2SH, 25°, 5-20 min H2S, 2 h, high yield. The removal of an 5-benzylthiomethyl protective group from a dithioacetal with mercuiy(II) acetate avoids certain side reactions that occur when an 5-benzyl thioether is cleaved with sodium/ammonia. The dithioacetal is stable to hydrogen bromide/acetic acid used to cleave benzyl carbamates. 

Thiols have been linked to insoluble supports as acid-labile benzyl thioethers, as aryl thioethers, as S-carbamoyl derivatives, and as unsymmetrical disulfides (Table 3.37). Because thiols often undergo oxidative dimerization in air to yield symmetric... 

Resin-bound benzylic thioethers can be converted into sulfonium salts by S-alkyla-tion with triethyloxonium tetrafluoroborate. These sulfonium salts react with palladium ) complexes to yield benzylpalladium complexes, which undergo Suzuki coupling with arylboronic acids (Entry 7, Table 3.48),... 

In striking contrast, when the reaction was carried out in methanol or benzene containing a small amount of a base such as aqueous NH3 or triethylamine (TEA) (Scheme 32), the N-2-C-3 interchange product, 4-phenylthiazole (52), was obtained in 90% yield along with a small quantity of the deprotonated photocleavage product (57), which was trapped by reaction with benzyl bromide to yield the ( /Z)-benzyl-thioether (58) <98JOC5592>. Conversion of 55-5d to 52-5d (Scheme 33) under these conditions confirmed that the transposition occurred via the... 

Many types of aromatic substrate are known to undergo a cyclometallation reaction when exposed to alkylpentacar-bonylmanganese complexes under thermal conditions. It is well established that the treatment of ligand appended arenes with alkylmanganesepentacarbonyl complexes can lead to the formation of [C,Y] heterochelates of Mn(CO)4 (Y being a two-electron donor ligand) (Equation 6). For instance, aromatic compounds such as W,W-dimethylbenzyl-amine, alkyl benzyl thioethers, 2-phenylpyridine, acetophenone, benzaldehyde, and diazobenzene can be readily... 

Trichloromethyl thioalkyl compounds of formula RSCXClj (a, b, X = Cl, R = Ph or CHjPh) as well as dichloromethyl benzyl thioether react with iron(II) tetraphenylporphyrin (TPP) (233), in the presence of a reducing agent (iron powder or Na2S204), to produce chlorocarbene complexes of type 234 (158). 

A number of other groups can be used for the protection of thiols benzyl thioethers of amino acids and peptides have been cleaved electrochemically at a platinum cathode in liquid ammonia [121], at mercury in MeOH-TMACl [122], and in DMF [123,124], and the trityl group has been used to protect cysteine cysteine was recovered in 90% yield after reduction in DMF [124]. The 4-pyridylmethyl [125,126] and diphenyl-4-pyridylmethyl groups can be cleaved in acid solution [124] at a mercury cathode. 

Proline was also ahached to crosslinked PS through a benzyl thioether linkage, as shown in Scheme 3.18. The PS-supported proline 62 was used as organocatalyst in the asymmetric aldol reachon between cyclohexanone 64 and subshtuted benzaldehyde 63 in water [41]. The reachon with p-cyanobenzaldehyde gave the aldol adduct in 98% conversion with a high level of enanhoselectivity (98% ee). The... 

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