A new, highly efficient Lewis base catalyst for a practical enantio- and diastereoselective crotylation of unsaturated aldehydes with E- and Z-crotyltrichlorosilanes has been developed. The method was employed as a key step in a novel asymmetric synthesis of bioactive serrulatane diterpene (−)-elisabethadione. Other strategic reactions for setting up the stereogenic centers included anionic oxy-Cope rearrangement and cationic cyclization. The synthetic route relies on simple, high yielding reactions and avoids use of protecting groups or chiral auxiliaries.

An efficient and practical Pd-catalyzed intramolecular oxidative allylic amidation provides facile access to derivatives of 1,3- and 1,4-amino alcohols and 1,3-diamines. The method operates under mild reaction conditions (RT) with molecular oxygen (1 atm) as the sole reoxidant of Pd. Excellent diastereoselectivities were attained with substrates bearing a secondary stereogenic center

A mild protocol has been developed for the Pd^II-catalyzed alkoxycarbonylation of terminal olefins to produce α,β-unsaturated esters with a wide range of substrates. Key features are the use of MeCN as solvent (and/or ligand) to control the reactivity of the intermediate Pd complexes and the combination of CO with O₂, which facilitates the Cu^II-mediated reoxidation of the Pd⁰ complex to Pd^II and prevents double carbonylation.

3-Chlorooxoindoles have emerged as versatile precursors in the synthesis of spirocyclopropyl oxindoles. High enantio- and diastereoselectivity was attained under conditions of both iminium/enamine and H-bonding catalysis.

Detailed kinetic and computational investigation of the enantio- and diastereoselective allylation of aldehydes 1 with allyltrichlorosilanes 5, employing the pyridine N-oxides METHOX (9) and QUINOX (10) as chiral organocatalysts, indicate that the reaction can proceed through a dissociative (cationic) or associative (neutral) mechanism: METHOX apparently favors a pentacoordinate cationic transition state, while the less sterically demanding QUINOX is likely to operate via a hexacoordinate neutral complex. In both pathways, only one molecule of the catalyst is involved in the rate- and selectivity-determining step, which is supported by both experimental and computational data.

Enantio- a diastereoselektivní allylace aldehydů 1 allyltrichlorsilany 5 s použitím derivátů pyridin-N-oxidu METHOX (9) a QUINOX (10) jako chirálních organokatalyzátorů byla detailně studována pomocí kinetických a výpočetních metod. Reakce může probíhat disociativním (kationtovým) nebo asociativním (neutrálním) mechanismem: v případě METHOXu je pravděpodobný pentakoordinovaný kationtový tranzitní stav, zatímco méně stericky náročný QUINOX zřejmě dává přednost neutrálnímu hexakoordinovanému komplexu. Experimentální i vypočtená data ukazují, že se kroku určujícího rychlost a selektivitu reakce účastní v obou případech pouze jedna molekula katalyzátoru.

Enantiopure, Boc-protected alkoxyamines 12 and 13, derived from the readily available homoallylic alcohols 4 via a reaction that involves either inversion or retention of configuration, undergo a diastereoselective Pd-catalyzed ring-closing carbonylative amidation to produce isoxazolidines 16/17 (≤50:1 diastereoisomer ratio (d.r.)) that can be readily converted into the N-Boc-protected esters of β-amino-δ-hydroxy acids and their γ-substituted homologues 37. The key carbonylative cyclization proceeds through an unusual syn addition of the palladium and the nitrogen nucleophile across the CC bond (1921), as revealed by the reaction of 15, which afforded isoxazolidine 18 with high diastereoselectivity.

A mild, simple oxidation protocol employing iron(III) chloride as a catalyst and hydrogen peroxide as a stoichiometric oxidant was found to be compatible with an intramolecular carbonyl nitroso ene reaction and allowed us to efficiently convert hydroxamic acids into a diverse range of 1,2- and 1,3-amino alcohol derivatives in a single operation.