- Thiophilic addition of organolithiums to trithiocarbonate oxides (sulfines). Synthesis of β-oxoketene dithioacetals, 1,4-dicarbonyl compounds, and allyl sulfoxides
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Reaction of trithiocarbonates with meta-chloroperoxybenzoic acid in CH2Cl2 at 0°C affords the corresponding S-oxides. These sulfines are relatively stable comppounds which can be purified by chromatography. They react readily with organolithiums in THF at -78°C in a thiophilic manner to give carbanions which are stabilized by three sulfur groups. Hydrolysis affords trithioorthoester oxides. The thermal behaviour of these hindered products has been investigated and new rearrangenrent processes have been evidenced. The former carbanions are soft nucleophiles: 1,4-addition of these intermediates to α-enones was achieved selectively to lead to β-oxo ketenedithioacetals, which are easily transformed into 4-oxoalkanethioates. This 'Umpolung' route allows the formal use of the (alkylthio)carbonyl anion. A thiophilic addition was also observed with allylsilanes in the presence of n-Bu4NF furnishing allyl sulfoxides.
- Leriverend, Catherine,Metzner, Patrick,Capperucci, Antonella,Degl'Innocenti, Alessandro
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p. 1323 - 1342
(2007/10/03)
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- THE REACTIONS OF SOME 1,1,1-TRIBROMO-ALKYL SYSTEMS WITH THIOLATE ANIONS
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Compounds containing a 1,1,1-tribromoethyl group are normally dehydrobrominated by reaction with sodium thiolates.If a 1,1,1-tribromobut-3-ene fragment is present cyclisation to a 2,2-dibromocyclopropylmethyl thioether or rearrangement are also observed.
- Baird, Mark S.,Hoorfar, Alireza,Mitra, Manjushri
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p. 2509 - 2512
(2007/10/02)
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- Electrochemical Reduction of Alkyl Aryl and Dialkyl Trithiocarbonates
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Electrochemical reduction in aprotic medium of alkyl aryl trithiocarbonates (1a-c) in the presence of an alkylating agent gives tetraalkyltetrathioethylenes (2a-c); under similar conditions dialkyl trithiocarbonates (3a-c) also form 2, but the reaction is complicated by the ability of 3 to act as an alkylating agent.The mechanisms of the reactions are discussed on the basis of the preparative and cyclic voltammetric results.
- Falsig, Mogens,Lund, Henning
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p. 545 - 550
(2007/10/02)
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