- Trithioorthoester Exchange and Metathesis: New Tools for Dynamic Covalent Chemistry
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To expand the toolbox of dynamic covalent and systems chemistry, we investigated the acid-catalyzed exchange reaction of trithioorthoesters with thiols. We found that trithioorthoester exchange occurs readily in various solvents in the presence of stoichiometric amounts of strong Bronsted acids or catalytic amounts of certain Lewis acids. The scope of the exchange reaction was explored with various substrates, and conditions were identified that permit clean metathesis reactions between two different trithioorthoesters. One distinct advantage of S, S, S-orthoester exchange over O, O, O-orthoester exchange is that the exchange reaction can kinetically outcompete hydrolysis, thereby making the process less sensitive to residual moisture. We expect that the relatively high stability of the products might be beneficial in future supramolecular receptors or porous materials.
- Bothe, Michael,Furlan, Ricardo L. E.,Orrillo, A. Gastón,Von Delius, Max
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supporting information
p. 1988 - 1994
(2019/10/22)
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- From C1 to C2: TMSCF3 as a Precursor for Pentafluoroethylation
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A highly efficient copper-mediated aromatic pentafluoroethylation method using TMSCF3 as the sole fluoroalkyl source is described. The reaction proceeds by a key C1 to C2 process, that is, the generation of CuCF3 from TMSCF3, followed by a subsequent spontaneous transformation into CuC2F5. Various aryl iodides were pentafluoroethylated with the TMSCF3-derived CuC2F5. This method represents the first practical and efficient method for pentafluoroethylation of aryl iodides using commercially available TMSCF3 as a pentafluoroethyl precursor.
- Xie, Qiqiang,Li, Lingchun,Zhu, Ziyue,Zhang, Rongyi,Ni, Chuanfa,Hu, Jinbo
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supporting information
p. 13211 - 13215
(2018/09/25)
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- A highly efficient carbon-sulfur bond formation reaction via microwave-assisted nucleophilic substitution of thiols to polychloroalkanes without a transition-metal catalyst
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An efficient carbon-sulfur bond formation reaction has been developed under microwave irradiation. This reaction affords a novel and rapid synthesis of thioacetals and sulfides under mild conditions. This method is particularly noteworthy given its experimental simplicity and high generality, and no transition-metal catalysts were needed under our conditions.
- Cao, Yi-Ju,Lai, Yuan-Yuan,Cao, Hong,Xing, Xiao-Ning,Wang, Xiang,Xiao, Wen-Jing
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p. 1529 - 1533
(2007/10/03)
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- 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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- CLAY CATALYSIS: SYNTHESIS OF ORGANOSULPHUR SYNTHONS
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The Montmorillonite KSF catalyses the synthesis of a large variety of organic sulphur compounds from carbonyl compounds: dithianes, thioacetals, thioketals,thiochromanes.
- Labiad, B.,Villemin, D.
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