4431-79-2Relevant academic research and scientific papers
Preparation method of dithioacetal derivative
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Paragraph 0029-0031, (2021/02/10)
The invention discloses a method for preparing a dithioacetal derivative, which specifically comprises the steps of sequentially adding sodium borohydride and thiophenol or mercaptan into a reaction tube filled with a dichloromethane solvent, sealing the
From Short-Bite Ligand Assembled Ribbons to Nanosized Networks in Cu(I) Coordination Polymers Built upon Bis(benzylthio)alkanes (BzS(CH2)nSBz; n = 1?9)
Fortin, Daniel,Harvey, Pierre D.,Knorr, Michael,Lapprand, Antony,Schlachter, Adrien,Strohmann, Carsten
supporting information, p. 3686 - 3708 (2020/03/19)
With the objective to establish a correlation between the spacer distance and halide dependence on the structural features of coordination polymers (CPs) assembled by the reaction between CuX salts (X = Cl, Br, I) and dithioether ligands BzS(CH2)nSBz (n = 1?9; Bz = benzyl), a series of 26 compounds have been prepared and structurally investigated. A particular attention has been devoted to the design of networks with extremely long and flexible methylene spacer units between the SBz donor sites. Under identical conditions, CuI and CuBr react with BzSCH2Bz (L1) affording respectively the one-dimensional (1D) CPs {Cu(μ2-I)2Cu}(μ-L1)2]n (CP1) and {Cu(μ2-Br)2Cu}(μ-L1)2] (CP2), which incorporate Cu(μ2-X)2Cu rhomboids as secondary building units (SBUs). The hitherto unknown architecture of two-dimensional (2D) layers obtained with CuCl (CP3) differs from that of CP1 and CP2, which bear inorganic ?Cl?Cu?Cl?Cu?Cl? chains interconnected through bridging L1 ligands, thus forming a 2D architecture. The crystallographic characterization of a 1D CP obtained by reacting CuI with 1,3-bis(benzylthio)propane (L2) reveals that [{Cu(μ2-I)2Cu}(μ-L2)2]n (CP4) contains conventional Cu2I2 rhomboids as SBUs. In contrast, unusual isostructural CPs [{Cu(μ2-X)}(μ2-L2)]n (CP5) and (CP6) are obtained with CuX when X = Br and Cl, respectively, in which the isolated Cu atoms are bridged by a single μ2-Br or μ2-Cl ion giving rise to infinite [Cu(μ2-X)Cu]n ribbons. The crystal structure of the strongly luminescent three-dimensional (3D) polymer [{Cu4(μ3-I)3(μ4-I)(μ-L3)1.5]n (CP7) issued from reacting 2 equiv of CuI with BzS(CH2)4SBz (L3) has been redetermined. CP7 features unusual [(Cu4I3)(μ4-I)]n arrays securing the 3D connectivity. In contrast, mixing CuI with an excess of L3 provides the nonemissive material [{Cu(μ2-I)2Cu}(μ-L3)2]n (CP8). Treatment of CuBr and CuCl with L3 leads to [{Cu(μ2-Br)2Cu}(μ-L3)2]n (CP9) and the 0D complex [{Cu(μ2-Cl)2Cu}(μ-L3)2] (D1), respectively. The crystallographic particularity for CP9 is the coexistence of two topological isomers within the unit cell. The first one, CP9-1D, consists of simple 1D ribbons running along the a axis of the unit cell. The second topological isomer, CP9-2D, also consists of [Cu(μ2-Br)2Cu] SBUs, but these are interconnected in a 2D manner forming 2D sheets placed perpendicular to the 1D ribbons. Four 2D CPs, namely, [{Cu4(μ3-I)4}(μ-L4)2]n (CP10), [{Cu(μ2-I)2Cu}(μ-L4)2]n (CP11), [{Cu(μ2-Br)2Cu}(μ-L4)2]n (CP12), and [{Cu(μ2-Cl)2Cu}(μ-L4)2]n (CP13), stem from the self-assembly process of CuX with BzS(CH2)6SBz (L4). A similar series of 2D materials comprising [{Cu4(μ3-I)4}(μ-L5)2]n (CP14), [{Cu(μ2-I)2Cu}(μ-L5)2]n (CP15), [{Cu(μ2-Br)2Cu}(μ-L5)2]n (CP16), and [{Cu(μ2-Cl)2Cu}(μ-L5)2]n (CP17) result from the coordination of BzS(CH2)7SBz (L5) on CuX. Ligation of CuX with the long-chain ligand BzS(CH2)8SBz (L6) allows for the X-ray characterization of the luminescent 2D [{Cu4(μ3-I)4}(μ-L6)2]n (CP18) and the isostructural 1D series [{Cu(μ2-X)2Cu}(μ-L6)2]n CP19 (X = I), CP20 (X = Br) and CP21(X = Cl). Noteworthy, BzS(CH2)9SBz (L7) bearing a very flexible nine-atom chain generated the crystalline materials 2D [{Cu4(μ3-I)4}(μ-L7)2]n (CP22) and the isostructural 1D series [{Cu(μ2-X)2Cu}(μ-L6)2]n CP23 (X = I), CP24 (X = Br), and CP25 (X = Cl), featuring nanometric separations between the cubane- or rhomboid-SBUs. This comparative study reveals that the outcome of the reaction of CuX with the shorter ligands BzS(CH2)nSBz (n = 1?4) is not predictable. However, with more flexible spacer chains BzS(CH2)nSBz (n = 6?9), a clear structural pattern can be established. Using a 1:1 CuX-to-ligand ratio, [{Cu(μ2-X)2Cu}(μ-L4?7)2] CPs are always formed, irrespectively of L4?L7. Employing a 2:1 CuX-tocontinued... ligand ratio, only CuI is able to form networks incorporating Cu4(μ3-I)4 clusters as SBUs. All attempts to construct polynuclear cluster using CuBr and CuCl failed. The materials have been furthermore analyzed by powder X-ray diffraction, Raman spectroscopy, and thermogravimetric analysis, and the photophysical properties of the emissive materials have been studied.
Straightforward chemoselective access to unsymmetrical dithioacetals through a thiosulfonate homologation-nucleophilic substitution sequence
Ielo, Laura,Pillari, Veronica,Gajic, Natalie,Holzer, Wolfgang,Pace, Vittorio
supporting information, p. 12395 - 12398 (2020/10/30)
A sequential C1-homologation-nucleophilic substitution tactic is presented for the preparation of rare unsymmetrical dithioacetals. The judicious selection of thiosulfonates as convenient sulfur electrophilic sources - upon the homologation event conducted on an intermediate a-halothioether - guarantees the release of the non-reactive sulfonate group, thus enabling the subsequent nucleophilic displacement with an external added thiol [(hetero)- aromatic and/or aliphatic]. Uniform high yields and excellent chemocontrol were deduced during the extensive scope study, thus documenting the versatility of the direct technique for the preparation of these unique and manipulable materials.
Sc(OTf)3-Catalyzed Synthesis of Symmetrical Dithioacetals and Bisarylmethanes Using Nitromethane as a Methylene Source
Dethe, Dattatraya H.,Shukla, Manmohan,Dherange, Balu D.
supporting information, p. 5778 - 5782 (2020/07/30)
Use of nitromethane as an electrophilic methylene source for the synthesis of symmetrical dithioacetals and bisarylmethanes has been showcased using Sc(OTf)3 as a catalyst. The procedure allows straightforward access to the densely functionalized dithioacetals and bisarylmethanes under mild conditions. Additionally, the method has been applied for the synthesis of antimalarial tetramethyl mellotojaponin C and anticancer dimeric phloroglucinol derivative.
Reduction of CO2 into Methylene Coupled with the Formation of C-S Bonds under NaBH4/I2 System
Guo, Zhiqiang,Zhang, Bo,Wei, Xuehong,Xi, Chanjuan
supporting information, p. 6678 - 6681 (2018/10/24)
A selective four-electron reduction of CO2 with thiophenol using NaBH4 as a reductant is described to access dithioacetals. This reaction provides a novel synthetic method for the highly selective conversion of CO2 into methylene, and a new access to molecular structures via formation of C-S bonds using CO2 as the C1 source.
Cs2CO3-promoted methylene insertion into disulfide bonds using acetone as a methylene source
Chen, Qian,Yu, Guodian,Wang, Xiaofeng,Huang, Yulin,Yan, Yan,Huo, Yanping
supporting information, p. 4086 - 4089 (2018/06/12)
An efficient halogen-free Cs2CO3-promoted methylene insertion into disulfide bonds has been achieved using acetone as a methylene source under mild conditions. This method provides a convenient and practical route to dithioacetals in up to 96% yield with good functional group compatibility.
Bromomethyllithium-mediated chemoselective homologation of disulfides to dithioacetals
Pace, Vittorio,Pelosi, Azzurra,Antermite, Daniele,Rosati, Ornelio,Curini, Massimo,Holzer, Wolfgang
supporting information, p. 2639 - 2642 (2016/02/18)
An efficient, chemoselective homologation of disulfides and diselenides to the corresponding dithio- and diselenoacetals has been developed via the addition of bromomethyllithium. Chemoselectivity is fully preserved in the presence of concomitant electrophilic sites decorating the substrates. The synthetic potential of selected dithioacetals has been evaluated in Feringa-Fa?anas-Mastral-type Pd-catalyzed coupling with an organolithium and in the unusual 1,4-addition to a Weinreb amide.
A highly efficient heterogeneous rhodium(I)-catalyzed C-S coupling reaction of thiols with polychloroalkanes or alkyl halides under mild conditions
Xia, Jianhui,Yao, Ruiya,Cai, Mingzhong
, p. 221 - 225 (2015/03/30)
Heterogeneous C-S coupling reaction of thiols with polychloroalkanes or alkyl halides was achieved at 30 or 80 °C in the presence of 5 mol% of an MCM-41-immobilized bidentate phosphine rhodium complex (MCM-41-2P-RhCl(PPh3)) and triethylamine, yielding a variety of formaldehyde dithioacetals, ethylenedithioethers and unsymmetric thioethers in good to excellent yields. This heterogeneous rhodium catalyst can be easily recovered and recycled by simple filtration of the reaction solution and used for at least 10 consecutive trials without significant loss of activity.
Sterically controlled synthesis and nucleophilic substitution reactions of di- and trimeric n-heterocyclic phosphenium metal(0) halides
Nickolaus, Jan,Bender, Johannes,Nieger, Martin,Gudat, Dietrich
, p. 3030 - 3036 (2014/07/21)
The reaction of symmetrical bis(diazaphospholenyl) compounds with [MCl 2(cod)] (M = Pd, Pt; cod = 1,5-cyclooctadiene) has been used to prepare N-heterocyclic phosphenium (NHP) metal(0) halides [M(NHP)Cl]n with diverse N substituents.
