Vladimír Hanuš

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.

A directly ring-to-ring linked ferrocene–pseudotitanocene complex

Abstract Addition of excess ferrocenylacetylene (FcCCH) to [η 5 -(C 5 H 5 )Ti][μ:η 2 :η 2 -C 2 (SiMe 3 ) 2 ] 2 [η 5 -(C 5 H 5 )Mg] ( 1 ) affords the novel ferrocene–pseudotitanocene complex [η 5 -1,2,5,6-tetrakis(trimethylsilyl)-4-ferrocenylcyclohexa-1,4-dienyl](η 5 -cyclopentadienyl)titanium(II), [η 5 -(Me 3 Si) 4 FcC 6 H 2 ]Ti(η 5 -C 5 H 5 ) ( 2 ), as the sole isolated titanium-containing product. Its structure was established by EI MS, NMR and UV–vis spectroscopy. The formation of 2 follows the general reaction route of terminal acetylenes with 1 .

Rearrangement and loss of bromine radical and CO from some bromobenzyl alcohols following electron ionisation

The electron ionisation spectra of bromine-containing derivatives of benzyl alcohol are often dominated by ions which do not contain bromine. We use the experimental data on a series of selected bromobenzyl alcohols to elucidate the easy loss of bromine atoms. In this process, arene-bonded bromines are displaced by hydrogens which originate from the benzyl group. Thus, we conclude that this reaction occurs during the “hydrogen ring-walk”. The suggested reaction mechanism and structures of intermediates, which can be considered, are discussed and graphically illustrated.