硫叶立德途径立体控制合成乙烯基型环氧化合物

在相转移条件下(CH3CN/KOH/RT)乙烯基型硫叶立德和醛反应高产率地得到以反式为主的产物,而在低温溴化锂存在下(LiBr/KHMDS/THF/-90℃)得到以顺式为主的产物,对于通过反应条件的变换而改变反应产物立体化学的机理,给出了一个初步的解释。     

The Rh(II) catalyzed reaction of diethyl diazomalonate with thietanes: a facile synthesis of tetrahydrothiophene derivatives via sulfonium ylides

A facile Rh(II) catalyzed reaction of diethyl diazomalonate with thietanes leading to highly substituted tetrahydrothiophenes along with allyl thioethers is described.     

A leap forward in sulfonium salt and sulfur ylide chemistry

Sulfonium salts and sulfur ylides are important S(Ⅳ) motifs,and have displayed many unique reactivities to provide simple,effective,and often stereoselective synthesis toward sulfur containing compounds.Impressive developments have been witnessed within this field during the past several years.In light of the increasing demand of organosulfur compounds across the range of chemical sciences,our aim of this review is to provide a concise overview of recent advances of sulfonium salt and sulfur ylide chemistry.Selected examples are organized in three parts on the basis of their role in organic reactions(reactants,intermediates and catalysts).     

Dimethyl(2-oxo-2-ferrocenylethyl)sulfonium iodide—a useful synthetic equivalent of ferrocenoylcarbene in the synthesis of ferrocene-containing cyclopropanes

The reaction of 1-ferrocenyl-3-thiabutan-1-one with methyl iodide in acetonitrile at room temperature gave dimethyl(2-oxo-2-ferrocenylethyl)sulfonium iodide, which was characterized by spectral data (¹H NMR, ¹³C NMR, IR) and X-ray crystallographic analysis. This salt reacted with a base (sodium hydride) in acetonitrile yielding a stabilized ylide—dimethylsulfonium ferrocenoylmethylide, which was in turn, submitted to reactions with seven conjugated enones. The obtained results showed that this methodology is potentially a new and useful approach to ferrocene-containing cyclopropanes.     

An expedient synthesis of ferrocene grafted spirooxindolopyrrolizidines via [3+2]-cycloaddition of azomethine ylides

A facile and rapid one-pot synthesis of ferrocene bearing novel spiropyrrolizidines has been accomplished by [3+2]-cycloaddition reaction of various azomethine ylides derived from isatin/5,7-dibromoisatin and l-proline with various ferrocene derivatives as dipolarophile in good yield. The protocol is general and applicable to a wide variety of ferrocenyl derived dipolarophiles. Effect of various solvents on [3+2]-dipolar cycloaddition reaction is also studied.     

An expedient synthesis of pyrrolidinyl spirooxindole grafted 3-nitrochromanes through 1,3-dipolar cycloaddition reaction of azomethine ylides

A facile one-pot synthesis of pyrrolidinyl-spirooxindole grafted 3-nitrochromanes has been accomplished by 1,3-dipolar cycloaddition (1,3-DC) reaction of 3-nitrochromenes with azomethine ylides generated in situ from isatin and secondary amino acids. The regio- and stereochemical outcome of the cycloaddition reaction was ascertained by X-ray crystallographic analysis.     

Cross-linking of Polymer of Intrinsic Microporosity (PIM-1) via nitrene reaction and its effect on gas transport property

Polymer of Intrinsic Microporosity (i.e. PIM-1) has been crosslinked thermally via nitrene reaction using polyethylene glycol biazide (PEG-biazide) as a crosslinker. The crosslinking temperature was optimized using TGA coupled with FT-IR spectroscopy. The dense membranes containing different ratios of PIM-1 to PEG-biazide were cast from chloroform solution. Crosslinking of PIM-1 renders it insoluble even in excellent solvents for the uncrosslinked polymer. The resulting crosslinked membranes were characterized by FT-IR spectroscopy, TGA and gel content analysis. The influence of crosslinker content on the gas transport properties of PIM-1, its density and fractional free volume (FFV) were investigated. Compared to the pure PIM-1 membrane, the crosslinked PIM-1 membranes showed better gas separation performance especially for CO₂/N₂, CO₂/CH₄ and propylene/propane (C₃H₆/C₃H₈) gas pairs and as well as suppressed penetrant-induced plasticization under high CO₂ pressure.     

Carbon-carbon bond-forming reaction of cyclic sulfonium ylides stabilized by a carbonyl group

Rhodium(II)-catalyzed decomposition of diazoketones 1 and 5 bearing a cyclic dithioacetal, in the presence of aldehyde and ClTi(Oi-Pr)(3), afforded both or one of the C=C-bonded products, i.e., ring-enlarged enone 2 and ring-transformed thiophenone 3, that were formed between aldehyde and intermediate bicyclosulfonium ylide. The stereochemistry of the exocyclic C=C bond in the products was exclusively Z. The sulfonium atom that transiently composed the ylide was incorporated into products, but no oxirane was formed.     

One-dimensional chloro-bridged Cd(II) chains separated by dimethyl hexadecyl sulfonium cation layers: synthesis and structure

A low-dimensional material with the composition {(n-C₁₆H₃₃)(CH₃)₂S}_∞ ⁺¹[CdCl₃]^? has been prepared. As expected, the sulfonium cations form an insulating organic layer; the closest Cd–Cd distance between layers is about 19 Å, as compared to 3.9 Å within the same layer. The inorganic layer is formed by a 5-coordinated cadmium(II) moiety CdCl₅, connected to a one-dimensional chain of slightly distorted, edge-sharing square pyramids. The compound was synthesized from the parent sulfonium chloride and CdCl₂ in ethanol, exploiting the Lewis acidity of Cd(II).     

An efficient synthesis of dihydro- and tetrahydropyrans via oxonium-ene cyclization reaction

An efficient method has been developed for the synthesis of 2,3-dihydropyrans and 4-methylenetetrahydropyrans from aldehydes and substituted homoallyl alcohols in benzene mediated by boron trifluoride etherate in good yields. The reaction proceeds via oxonium-ene reaction.     

An expedient diastereoselective synthesis of pyrrolidinyl spirooxindoles fused to sugar lactone via [3+2] cycloaddition of azomethine ylides

Synthesis of pyrrolidinyl-spirooxindoles fused to sugar lactone has been achieved by a one pot three component 1,3-dipolar cycloaddition (1,3-DC) reaction. A unique dipolarophile (α,β-unsaturated lactone) derived from d-glucose/d-galactose reacted with azomethine ylide generated in situ from isatin/N-substituted isatin and secondary amino acids (sarcosine/proline/piperidine-2-carboxylic acid) to give the corresponding cycloadducts in good yield. The cycloaddition was found to be highly regio- and diastereoselective.     

Highly diastereoselective synthesis of dispiro[1,4-dithiane/dithiepane]bisoxindoles via Stevens rearrangement

Synthesis of dispiro[1,4-dithianes/dithiepanes]bisoxindoles from the reaction of 3-diazo-2-oxindoles and spiro-1,3-dithiolaneoxindole or -1,3-dithianeoxindole derivatives in the presence of rhodium(II) acetate dimer as a catalyst was demonstrated under mild conditions in a highly diastereoselective manner. These dispiro-compounds were obtained via intermolecular sulfonium ylides and followed by Stevens rearrangement.     

Rhodium(II)-catalyzed addition of 2-diazo(fluoroalkyl)acetoacetates to sulfides: a simple synthesis of stable sulfonium ylides

2-Diazo(fluoroalkyl)acetoacetates 1 reacted readily with many sulfides under mild reaction conditions in the presence of catalytic Rh₂(OAc)₄ affording to the corresponding sulfonium ylides. While thianthrene gave trans-thianthrenium 5,10-di(fluoroalkylacetoethoxycarbonyl)methylides (7a and 7b) under the same reaction condition, the structure of 7btrans-thianthrenium 5,10-di(bromodifluoroacetoethoxy-carbonyl)methylides was fully confirmed by spectral methods and X-ray single crystal diffraction analysis. All the ylide products obtained are fairly stable due to the strong electron-withdrawing properties of the fluorine atom.     

An expedient regio and diastereoselective synthesis of novel spiropyrrolidinylindenoquinoxalines via 1,3-dipolar cycloaddition reaction

We described an efficient and multicomponent approach for the synthesis of novel polyheterocyclic spiropyrrolidinylindenoquinoxalines via 1,3 dipolar [3+2] cycloaddition reaction of 3-methyl-4-nitro-5-alkenylisoxazoles, ninhydrin, orthophenylenediamine and benzyl amine. Excellent to good yields were obtained. Various isoxazole derivatives were used as dipolarophiles against substituted benzylamine and o-phenylenediamine. Diastereoselectivity was found to be variable and found to be dependent on the substitutions and their position on the aromatic ring of the reactants. This catalyst free and green approach is column free and does not even require a work up procedure.     

X-ray crystal structure and spectral characterization of pseudo five-coordinate Hg(II) polymeric and four-coordinate binuclear complexes of an ambidentate sulfonium ylide

The reaction of ambidentate sulfonium ylide (Me)₂SCHC(O)C₆H₄-p-OCH₃(Y) with HgX₂ [X = Cl (1), Br (2) and I (3)] in equimolar ratios using methanol as the solvent leads to two types of products. Single-crystal X-ray diffraction analysis reveals (i) a two-dimensional polymer, [{HgCl₂(Y)}₄]_n, in which the mercury(II) atom is five-coordinated and ligand Y displays C-coordination as well as an additional interaction, including O-coordination to different mercury centers and (ii) an asymmetric halide-bridged binuclear structure of the type [HgBr₂(Y)]₂, in which the mercury(II) center is four-coordinate and ligand Y displays C-coordination to the metal. The characterization of these compounds by IR, ¹H- and ¹³C NMR spectroscopy confirms the coordination of the ylide to the metal through the carbon atom. Analytical data indicate a 1:1 stoichiometry between the ylide and the Hg(II) halide in all complexes.     

An efficient route to polynitrogen-fused tricycles via a nitrene-mediated N-N bond formation under microwave irradiation

The synthesis of unprecedented fused azaheterocyclic ring systems is described. Tricycles with either a central pyrazole or a triazole ring were obtained via a nitrene-mediated reaction of nitro bis(hetaryl) derivatives in the presence of triethylphosphite. The cyclization proceeded with complete chemoselectivity for the desired N-N bond formation and was completed within minutes under microwave activation. The key nitro bicycles were synthesized using either Stille couplings or aromatic nucleophilic substitution.     

An efficient synthesis of dienic nucleoside analogues via a Mitsunobu reaction

Nucleoside analogues 9 and 12 were obtained in good yields from alcohol 7 which, under Mitsunobu conditions, led to the title products after deprotection steps.     

Use of sulfonium ylides in the synthesis of heterocyclic systems (review)

The literature on the use of sulfur ylides in the synthesis of heterocyclic systems of varied structure is reviewed. The possible preparative value of these reactions is discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 147–173, February, 1990.     

The structure of sulfonium ylides stabilized by the malonylide moiety

The crystal structures of four thioxanthenium bis(carbomethoxy)methylides and methylides of di-(p-nitro-phenyl)sulfonium and dimethylsulfonium have been determined. The carbanion moiety in all cases is planar and the pi-system is rotated 90° with respect to the sulfur lone pair. All compounds exhibit a pseudo-equatorial orientation of the carbanion system except for the 2,4-dimethylthioxanthenium ylide. The compounds are described in terms of the geometries around the sulfur atom, the interplanar angles and sulfur-oxygen and oxygen-oxygen interactions. Surprisingly, the sulfur atom is not symmetrically placed with respect to the two phenyl rings in the thioxanthenium compounds. The sulfur is coplanar with one phenyl ring but is significantly out of the plane of the other. The ¹³C and ¹H spectra of the ylides are discussed along with the temperature dependence which indicates restricted rotation about the ⁺S? C^? bond in several cases. The factors contributing to the stability of the ylides are analyzed.