Štěpán Vyskočil

Transition metal catalysed synthesis of tetrahydro derivatives of [5]-, [6]- and [7]helicene

Abstract Tetrahydro analogues of [5]-, [6]- and [7]helicene have been easily prepared by intramolecular [2+2+2] cycloisomerization of appropriate triynes under CpCo(CO) 2 /PPh 3 or Ni(cod) 2 /PPh 3 catalysis. This nonphotochemical methodology allows enantioselective synthesis of a helical skeleton employing the Ni(cod) 2 /(S)-(−)-MOP catalytic system. On reaction with DDQ, tetrahydro[5]helicene was transformed to [5]helicene.

Synthesis of 2-amino-2′-diphenylphosphino-1,1′-binaphthyl (MAP) and its accelerating effect on the Pd(0)-catalyzed N-arylation

The title compound 3, synthesized in four steps from NOBIN (1), has been found to exhibit a dramatic accelerating effect on the Pd(0)-catalyzed Hartwig-Buchwald N-phenylation of amino alcohol 1 and diamine 8 with PhBr. Partial kinetic resolution was observed for the phenylation of (±)-1 or (±)-8 in the presence of (S)-BINAP.

Transition metal catalysis in organic synthesis: reflections, chirality and new vistas

The power of transition metal catalysis as a tool in organic synthesis is exemplified by the recent progress in the following areas: (i) diastereocontrol of Pd(0)-, Mo(0)-, and Ni(0)- catalyzed allylic substitution; (ii) Pd(0)-catalyzed asymmetric allylic substitution; (iii) Hartwig-Buchwald amination; and (iv) Suzuki coupling. Development of novel, bidentate binaphthyl ligands (MAP) and their unique mode of P,Cs-coordination is also described.

AXIALLY CHIRAL 1,1'-BINAPHTHYLS WITH NON-IDENTICAL GROUPS IN 2,2'-POSITIONS. SYNTHESIS OF THE ENANTIOMERICALLY PURE 2-HYDROXY-2'-THIOL AND SUBSTITUTED 2-AMINO-2'-THIOLS

Abstract Enantiomerically pure hydroxy thiol (S)-(+)- 6 , amino thiol (S)-(+)- 12 , and N , N -dimethylamino thiol (S)-(−)- 16 have been synthesized from BINOL (S)-(−)- 1 and the amino alcohol (S)-(−)- 7 , respectively, via the Newman-Kwart rearrangement of the corresponding thiocarbamoyl derivatives (S)-(−)- 2 , (S)-(−)- 10 , and (S)-(−)- 14 . Configurational stability of the binaphthyl unit has been observed.

On the ‘Novel two-phase oxidative cross-coupling of the two-component molecular crystal of 2-naphthol and 2-naphthylamine’

The FeCl3-mediated, heterogeneous cross-coupling of the title compounds (1 + 2 → 3) has been re-examined and formation of the molecular crystal (1 + 2) shown to be irrelevant to the selectivity observed; a comparison of FeIII and CuII as reagents is presented.