Alcohols mercapto

Meisenheimer rearrangement 52f. 1,2-mercapto alcohol 236 f. merrilactone A 241 (-) -mesembrine 306 metal etiolates... 

Derivatives of Mercapto Alcohols, Amino Alcohols and Diamines... 

Thiourea wae investigated with several epoxides, and found to bo a fairly satisfactory replacement for hydrogen sulfide in the preparation of /J-mercapto alcohols. Thus, propylene oxide, cyclcpentene oxide, cyolohexene oxide, and 1,2-epoxy-3-butene could be converted into the corresponding jg-mereapto alcohols (Eqe. 684 and 686). An improved... 

Node, M., Nishide, K., Shigeta, Y., Shiraki, H., Obata, K. A Novel Tandem Michael Addition/Meerwein-Ponndorf-Verley Reduction Asymmetric Reduction of Acyclic a,P-Unsaturated Ketones Using A Chiral Mercapto Alcohol. J. Am. Chem. Soc. 2000, 122,1927-1936. 

Figure 2. Synthesis pathway to 2-alkyl-3-mercapto alcohols...

In the early years of penem and carbapenem research, the easy preparation and commercial availability of azetidinone 10 prompted the devisal of several protocols for its conversion into an optically active equivalent (Scheme 1, F). Thus, acetate displacement with thioglycolic acid and resolution with d-( +)-ephedrine gave the 4/ -carboxymethylthio derivative 94, in turn elaborated to 95a [44], the 4R-enantiomer of the key intermediate of Woodward s first synthesis of racemic 6a-hydroxyethylpenems [45]. In another approach, analog 95b was obtained by diastereomer separation after displacement of 4-acetoxy-azetidinone with a chiral mercapto-alcohol [46]. Along a still different approach [43], optically active 93b was obtained from racemic 10 and thiophenol via asymmetric induction from the reaction medium (cinchonidine-containing benzene). 

Condensation of an ethylene dihalide with an alkali metal sulfide was studied in the latter part of the nineteenth century. The acid catalyzed polycondensation of certain mercapto alcohols represents a second method of synthesis. 

The first work on the self-assembly of gold colloid particles capped with alkanethiols was done by Brust and coworkers [Netzer, L, 1983]. This routine has been adopted by other scientists for the deposition of self-assembled monolayers of different colloid nanopartides (e.g., Ag, CdS, CdSe, and ZnS), which were prepared using mercapto-alcohols, mercaptocarboxylic acids, and thiophenols as capping agents. Self-assembled nanopartides usually show well-ordered lateral structures, proved by numerous observations with SEM, STM, and AFM [Collier. C, 1997, Lover. T, 1997, Rogach. A. L, 1999 and Vogel. W, 2000]. 

The first cyclic sulphenate (109) has been reported. This compound was prepared in 85% yield by the reaction of the mercapto-alcohol (110) with Brj in CCI4 containing pyridine at - 5 °C. The reaction of (109) with water or moist air gave the corresponding sulphinate, while treatment with 2 equivalents of the potassium salt of hexafluoro-2-phenylpropan-2-ol afforded the sulphurane (111). 

Reaction with Thiocarboxylic Acids, Phosphoric Acids, Sulfonic Acids, and their Derivatives. Thiocarboxylic acids, - dithiocarboxylic acids, and dimethyldithiocarbamic acid zinc salt, as well as various phosphorus oxyacids and phosphorus thioacids, can also be utilized. a,o)-Mercapto alcohols form cyclic thioethers whereas thiols react with both DEAD and TPP-DEAD to form disulfides. 2-Mercaptoazoles also react with alcohols in the presence of DEAD and TPP. Although arenesulfonic acids do not enter into the reaction, a combination of DEAD-TPP with methyl p-toluenesulfonate as a nucleophile carrier gives the corresponding alkyl sulfonates (eq 14). Altema-... 

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