The synthesis of unsymmetrical diaryl ketones via the Fukuyama coupling of thioesters and organozinc reagents is described. Typically, the synthesis of diaryl ketones using this methodology provides low yields. The simple complex, Pd(dba)(2), was found to convert a variety of aryl thioesters to diaryl ketones in good yields.

Peptidyl prolyl thioesters, which have been regarded as too unreactive for practical use in native chemical ligations (NCLs), were proven to be versatile reagents in peptide coupling. Tuning the reactivity of prolyl thioesters enabled a one-pot/sequential NCL reaction based on kinetically controlled ligation.

The occurrence of thioesterases hydrolyzing thioesters of monothiol coenzymes, e.g. glutathione (l-3) and wenzyme A (P6), is well documented. In the course of experiments on the metabolism of acetoacetyl thioesters (7), it was found that liver enzyme fractions catalyzed the hydrolysis of (f)-S-acetoacetyl6 ,E&dithioloctanoic(dihydrolipoic) acid (Reaction 1) and ( &S-acetyld, Sdithioloctanoic(di...

Direct organocatalytic Mannich-type reactions of thioesters provide for the expedient and diastereoselective synthesis of protected beta-amino acids. A variety of thioesters were found to be reactive with different imines under mild conditions to provide beta-amino acids in good yields. This chemistry was extended to a diastereo- and enantioselective variant.

A conjugate reduction of α,β-unsaturated thioesters catalyzed by copper hydride using PMHS as stoichiometric reductant has been developed. 1,2-Bis(diphenylphosphino)benzene (BDP) was the most effective ligand for this reduction. Saturated thioesters could be produced in excellent yields when the substituent on the thiol is not sterically-demanding. This protocol was applied to induce the reduct...

The direct addition of enolizable aldehydes and α-halo thioesters to produce β-hydroxy thioesters enabled by reductive soft enolization is reported. The transformation is operationally simple and efficient and has the unusual feature of giving high syn-selectivity, which is the opposite of that produced for (thio)esters under conventional conditions. Moreover, excellent diastereoselectivity res...

The β-amino carboxylic acid moiety is a key feature of numerous important biologically active compounds. We describe a syn-selective direct Mannich addition reaction that uses α-iodo thioesters and sulfonyl imines and produces β-amino thioesters. Enolate formation is achieved by reductive soft enolization. The products of the reaction provide straightforward access to biologically important β-l...

Addition of oleoyl-CoA (1 microM), or other acyl-CoA thioesters with a chain length of C(16) or greater, to oilseed rape plastids (Brassica napus L.) inhibited the rate of D-glucose 6-phosphate (Glc6P) uptake by 70% after 2 min. The IC(50) value for oleoyl-CoA inhibition of the transporter was approx. 0.2-0.3 microM. Inhibition was alleviated by the addition of acyl-CoA binding protein (ACBP) o...

A practical method to synthesize sulfinate esters from aryl iodides is disclosed. Direct oxidation of thioesters prepared by copper-catalyzed C–S formation realized the efficient synthesis sulfinate...