Electrophilic Oxidation of Stereodefined Polysubstituted Silyl Ketone Aminals

Abstract

Abstract:We reported herein a practical approach to acyclic tertiary α-hydroxy carbonyl compounds in only two chemical steps from alkynes with excellent diastereoselectivity through

ADUC Prizes: U.‐P. Apfel, P. Heretsch, O. Hollóczki / Carl Duisberg Memorial Award: B. Morandi / Elected to the Académie des Sciences: E. Charpentier, J. Cossy, I. Marek / Max Delbrück Junior Prize: S. Disch / Novartis Early Career Award: B. Morandi and R. R. Knowles

“…Marek and his team are interested in developing carbon–carbon‐bond‐forming processes that efficiently create multiple stereocenters in a single‐pot operation at a distant position from the most reactive functional group of the molecule. He is reported in Angewandte Chemie on asymmetric copper‐catalyzed carbomagnesiation of cyclopropanes, and in the European Journal of Organic Chemistry on the electrophilic oxidation of silyl ketone aminals . Marek is on the International Advisory Board of Angewandte Chemie , and is also on the editorial or advisory boards of Advanced Synthesis & Catalysis , Chemistry—A European Journal , the European Journal of Organic Chemistry , Helvetica Chimica Acta , the Israel Journal of Chemistry , and The Chemical Record .…”

Rearrangement ofN-tert-Butanesulfinyl Enamines for Synthesis of Enantioenriched α-Hydroxy Ketone Derivatives

“…C–O bonds can be formed enantioselectively using chiral auxiliaries and asymmetric catalytic methods ranging from organocatalysis − to metal-complex catalysis. , However, these methods of enantioselective α-oxygen functionalization usually work well only with carbonyl substrates that easily form stereodefined enols or enolates, such as α-monosubstituted carbonyls, cyclic α-branched carbonyls, or acyclic α,α-disubstituted carbonyls bearing two α-substituents differing greatly in bulkiness, such as an aryl group and an alkyl group . These methods do not work well with α,α-disubstituted carbonyls containing two α-substituents of similar bulkiness, such as two linear alkyl groups. , …”

Addition–Rearrangement of Ketenes with Lithium N-tert-Butanesulfinamides: Enantioselective Synthesis of α,α-Disubstituted α-Hydroxycarboxylic Acid Derivatives

“…Nevertheless, Davis and co-workers achieved some success in such functionalizations using double-asymmetric induction involving diastereoselective oxidation of chiral acyclic, polysubstituted enolates with chirality-matched camphorylsulfonyl oxaziridines. Subsequently, several examples of enantioselective construction of tertiary α-hydroxy carbonyls via oxidation of stereodefined acyclic enolates or their analogues have been reported. − …”