A very short and efficient synthesis of the important drug candidate telaprevir, featuring a biocatalytic desymmetrization and two multicomponent reactions as the key steps, is presented. The classical issue of lack of stereoselectivity in Ugi- and Passerini-type reactions is circumvented. The atom economic and convergent nature of the synthetic strategy require only very limited use of protect...

The first organocatalytic asymmetric assembly of Morita-Baylis-Hillman carbonates of isatins and α-angelica lactone has been studied, affording multifunctional products containing two valuable pharmacophores and vicinal quaternary chiral centers in high stereoselectivity (up to 92% ee, dr >95:5).

Under pre-activation glycosylation conditions, the 4,6-di-O-acetyl-N-acetyloxazolidinone protected donor afforded either excellent beta- or alpha-stereoselectivity simply by means of the addition of hindered base TTBP or the absence of base, leading to the controllable stereochemistry of coupling reactions.

Methods for the enantioselective conversion of D-xylose to differentially protected myo-inositol and L-chiro-inositol have been developed. The key transformation is a highly diastereoselective intramolecular SmI(2)-promoted pinacol coupling. The stereoselectivity was extremely dependent on the conditions, suggesting a change in mechanism. Preliminary mechanistic experiments and possible explana...

Density functional theory (DFT) has been used to investigate the α-alkylation of a chiral tricyclic ketone. These calculations reveal that torsional strain and a strong conformational preference, rather than steric influences, are responsible for the high levels of observed stereoselectivity and suggest a way by which alternative stereoisomers could be accessed.

A Pd-catalyzed addition of boronic acids to ynol ethers has been realized, delivering trisubstituted vinyl ethers in good yields with perfect control of the regio- and stereoselectivity. The reaction proceeds under mild conditions and exhibits excellent functional group compatibility. Moreover, the resultant products can be converted into pentasubstituted benzenes via the tandem Diels-Alder/aro...

The Au(I)-catalysed rearrangement of propargylic esters formed from an ynamide has been studied. The reaction is facile, and when conducted in the presence of a reactive indole nucleophile, leads to a cascade process whereby γ-indolyl α-acyloxyenamides are formed in good yield and excellent E-stereoselectivity.

The Ir(III) complex [Ir(2)H(2)I(3)((rac)-Binap)(2)](+)I(-) efficiently promotes the selective dimerization of 1,6-, 1,7-enynes and functionalized alkynes. This catalytic process results in the formation of head-to-head isomers with (E)-stereoselectivity. Subsequent Rh-catalyzed cycloisomerization under reductive conditions led to the corresponding 1,2-dialkylidenecyclopentane derivatives.

A novel ammonium iodide-induced sulfonylation of alkenes with DMSO and water toward the synthesis of vinyl methyl sulfones is described. The process proceeded smoothly under metal-free conditions with high stereoselectivity and good functional group tolerance. The reaction mechanism was revealed to proceed through a domino reaction of oxidation and elimination after the radical addition to alke...

An unprecedented Pd-catalyzed trans-addition of boronic acids to ynamides has been reported, giving α,β-disubstituted enamides in high yields with excellent regio- and stereoselectivity. A possible mechanism involving the palladium carbene intermediate has been proposed to account for the unusual trans-addition.