Reactivity of .beta.-Amino Alcohols with Carbon Disulfide Study on the Synthesis of 2-Oxazolidinethiones and 2-Thiazolidinethiones

Stereospecific Benzyne‐Induced Olefination from β‐Amino Alcohols and Its Application to the Total Synthesis of (−)‐1‐Deoxy‐D‐fructose

“…[11] Compound 2 a was then added to a solution of 2-silylphenyl triflate (3) and CsF in acetonitrile at room temperature for 4.5 h to give allylindole 4 a in 81 % yield. By using the same procedures, (2S)-3-(1H-indol-3-yl)propanol 1 b was also successfully converted to allylindole 4 b from 2 b (Scheme 1).…”

“…Under the same conversion conditions as described before, we did not generate any 1,3-thiazolidine-2-thione 25 via the intermediates 23 and 24 (see Scheme 7). Instead, a different heterocyclic compound 27 [11] containing an oxygen atom was produced in 78 % yield. This 1,3-oxazolidine-2-thione did not undergo a benzyne-induced elimination to give the corresponding olefin.…”

Crystal structure of (S)-3-(Z-1′,3′-butadienyl)-4-phenylthiazoline-2-one, C13H13NOS, a chiral 1-amino-diene useful in Diels-Alder cycloaddition reactions

“…Our interest in asymmetric Diels-Alder cycloadditions [5,6] led us to consider the preparation of 1-amino-1,3-butadiene equipped with such chiral auxiliaries. Starting from chiral 4-phenyl-oxazolidin-2-thione [2], and 1,4-dibromo-2-butene in the presence of a strong base, we always recovered 4-phenyl-thiazolidin-2-one derivatives [1] resulting from S-alkylation reaction (instead of N-alkylation) followed by heterocyclic rearrangement of the initially formed D 2 -1,3-oxazoline [7]. This formally S-O transposition reaction has been unambiguously proved by X-ray diffraction analysis of the resulting chiral aminodiene, namely the titled compound.…”

“…The titled compound was obtained by treatment of (S)-3-(4¢-bromobut-2¢-en-1¢-yl)-4-phenylthiazolidin-2-one with potassium tert-butoxide in THF solution at 293 K for 17 hours [1,2]. It was purified by column chromatography on silica gel (elution with cyclohexane/ethyl acetate 85/15; yield 51%) to furnish a white solid which was recrystallized from toluene (mp 375 K -376 K).…”

Crystal structure of bis(2-hydroxyethyl(phenyl)carbamodithioate)nickel(II), C18H20N2NiO2S4

“…Dithiocarbamate ligands can exist in different stable contributing resonance structures, which dictate the primary mode of bonding for different metals [9]. Dithiocarbamates are produced from the reaction between carbon disulfide and a secondary amine in the presence of a base [10]; the use of amino alcohols have by comparison rarely been used in the preparation of dithiocarbamates and its complexes [11,12]. The crystal structure of the title compound contains a 2-hydroxyethyl(phenyl)carbamodithioate ligand and one half of a Ni(II) in the asymmetric unit.…”