The [2,3]-sigmatropic rearrangement of allylic sulfoxides to allylic sulfenates is a reversible process, generally shifted toward the sulfoxide. In the presence of thiophiles, the sulfenate is trapped, and allylic alcohols are obtained under mild conditions. In most cases, a good transfer of stereochemical information through an ordered transition state is obtained. Furthermore, the ease of coupling this process with other versatile, stereocontrolled reactions has enhanced the usefulness of this protocol. This review aims to provide a comprehensive survey of this rearrangement and its application in the synthesis of natural and bioactive products.

Mesoionic carbenes (MICs) derived from triazolium salts that contain chiral sulfoxide or sulfoximine functional groups were used to construct enantiopure chiral-at-metal Ir and Rh half-sandwich complexes through the synthetic sequence of MIC complexation/C-H aromatic activation. The process was efficient and diastereoselective for the formation of enantiopure five-membered metallacycles. The use of the enantiomers of the chiral sulfur groups allowed us to prepare complexes that had opposite configurations at the metal center. Complete retention of the configuration at the metal center was observed during the formation of cationic Ir complexes and upon insertion of alkynes into the Ir -C bond, as demonstrated by a combined circular dichroism/X-ray study. These results point to a vicinal-assisted S 1-like mechanism.

The highly diastereoselective conjugate addition of alcohols and amines (RXH) to enantiopure 2-sulfinyl dienes renders transient allylic sulfoxides which undergo sulfoxide-sulfenate rearrangement and sulfenate cleavage providing 2-ene-1,4-diols and 2-ene-1,4-aminoalcohols with up to 99:1 dr. The method allows for the generation of two stereocenters in a single synthetic operation with remote chirality transfer of one center into the other.

An NMR comparative study of 1,2,3-triazole and triazolium anion recognition units containing sulfoxide, sulfone, and sulfoximine groups at C unveils an enhancement in binding ability up to ≈1 kcal/mol in acetone-d correlated with a theoretical increase of H acidity. DFT calculations provide insight into binding modes in line with experimental data for these receptors.

The highly diastereoselective sulfa-Michael addition of thiolates to enantiopure 2-sulfinyl dienes leads to anti or syn 2-ene-1,4-hydroxy sulfides in good yields and selectivities dependent on the reaction conditions in a diastereodivergent process. Synthetic applications of these enantiopure hydroxy sulfides by subsequent sigmatropic rearrangements have been outlined.

The first total synthesis of the natural alkaloid amphorogynine C is reported (2.9 % overall yield in 20 steps). The key steps include a Claisen–Johnson rearrangement and an intramolecular azide–olefin cycloaddition, followed by a reduction of the resulting imine. The construction of the pyrrolizidine skeleton was achieved by an alkoxide‐mediatedlactone ring opening and subsequent cyclization of a conveniently functionalized bicyclic amine. Finally, the proposed structure of amphorogynine C was confirmed by single‐crystal X‐ray diffraction analysis.

Herein, we describe the catalytic enantioselective cross-coupling of 1,2-bisboronic esters. Prior work on group specific cross coupling is limited to the use of geminal bis-boronates. This desymmetrization provides a novel...

A cascade intramolecular azide‐alkene 1,3‐dipolar cycloaddition/Stork alkylation reaction has been developed for the synthesis of functionalized cyclic imines with a pyrroline and piperideine structures, employing readily available ω‐azidodienes.