In the presence of 2.5 mol% Pd2(dba)3-TMEDA (1 : 4), a range of enantioenriched allylic alcohols smoothly coupled with boronic acids in a highly regioselective fashion with inversion of configuration to afford structurally diverse alkenes in good yields with perfect retention of ee.

A highly stereoselective BF3∙OEt2-promoted tandem hydroamination/glycosylation on glycal scaffolds has been developed to form propargyl 3-tosylamino-2,3-dideoxysugars in a one-pot manner. Subsequent construction of multivalent 3-tosylamino-2,3-dideoxyneoglycoconjugates with potential biochemical applications was presented herein involving click conjugations as the key reaction step. The copper-...

A highly enantioselective direct Mannich reaction of methyl alkyl ketones with cyclic imines benzo[e][1,2,3]oxathiazine 2,2-dioxides, catalyzed by the combination of cinchona alkaloid derived primary amine and TFA, is disclosed. For unsymmetrical methyl alkyl ketones, it is favoured that specific regioselective addition to the imine substrates occurs at the less-substituted methyl group by ster...

The synthesis of α-aminosilanes by a highly enantio- and regioselective copper-catalyzed hydroamination of vinylsilanes is reported. The system employs Cu-DTBM-SEGPHOS as the catalyst, diethoxymethylsilane as the stoichiometric reductant, and O-benzoylhydroxylamines as the electrophilic nitrogen source. This hydroamination reaction is compatible with differentially substituted vinylsilanes, thu...

The first report of a biocatalytic regioselective oxidative mono-cleavage of dialkenes was successfully achieved employing a cell-free enzyme preparation from Trametes hirsuta at the expense of molecular oxygen. Selected reactions were performed on a preparative scale affording high to excellent conversions and chemoselectivities.

The first regioselective ortho-lithiation at the 4-position of simple pyridine derivatives containing a 3-oxetane unit has been achieved using n-butyllithium as base. Electrophilic quenching of the resulting lithio species provides a rapid access to a broad range of new functionalized pyridine oxetane building blocks.

A nucleophilic catalysis method providing a concise synthesis of di-, tri-, and tetrasubstituted pyrroles is described. This regioselective one-pot method relies on nucleophilic catalysis of the intermolecular addition of oximes to activated alkynes and thermal rearrangement of the in situ generated O-vinyl oximes to form pyrroles that contain a functional group handle at the C3/C4 position.

We report the first synthesis of a natural (±)-gnetulin and an unnatural analogue of (±)-gnemonol M by using the regioselective oxidative coupling reactions of 5-tert-butyl-isorhapontigenin as the key step. Both the effects of different enzyme-catalyzed systems on the structures of coupling products and structural transformations of coupling products in the presence of several Lewis acids were ...

Epoxides and aziridines are common intermediates in synthesis. Readily accessible in enantioenriched form, they are typically used as electrophiles, taking advantage of their predictable highly regioselective ring-opening reactions. Our work in the area of α-lithiated terminal epoxides and aziridines indicates that there are many other less conventional but useful reactions of these small-ring ...

We report lipase catalysed regioselective inclusion of gastrodigenin (p-hydroxybenzyl alcohol: HBA) to a peptide Nmoc-Leu-Trp-OH at physiological pH 7.4. The resultant Nmoc-Leu-Trp-HBA from a reaction cycle of dissipative self-assembly evolves into blue light emitting peptide nanofibers.