2786-07-4

Usage

Uses

2-Thienyl-lithium is a useful building block for organic synthesis.

InChI:InChI=1/C4H3S.Li/c1-2-4-5-3-1;/h1-3H;/rC4H3LiS/c5-4-2-1-3-6-4/h1-3H

Upstream product

• 188290-36-0 thiophene 
• 109-72-8 n-butyllithium 
• 1003-09-4 2-bromothiophene 
• 3437-95-4 2-Iodothiophene 

Downstream Products

• 34243-33-9 2-thiophen-2-yl-quinoline 
• 6165-68-0 thiophene boronic acid 
• 100885-90-3 2-methyl-2-phenyl-1-[2]thienyl-propan-1-one 
• 101431-05-4 2-ethyl-2-phenyl-1-[2]thienyl-butan-1-one 
• 18557-51-2 phenyl-tri-[2]thienyl-silane 
• 18676-80-7 bis(2-thienyl)diphenylsilane 
• 17940-73-7 tetrakis(2-thienyl)silane 
• 101781-50-4 2-(1-methyl-[2]piperidyl)-1-phenyl-1-[2]thienyl-ethanol 
• 106302-20-9 2-(8-methyl-nortropan-3-endo-yl)-1-phenyl-1-thiophen-2-yl-ethanol 
• 66464-25-3 4,4-dimethyl-2-(2-(thiophene-2-yl)phenyl)-4,5-dihydrooxazole 
• 33266-43-2 1-isopropyl-5-phenyl-4-thiophen-2-yl-3,4-dihydro-1H-pyrimidin-2-one 
• 57242-36-1 5,8-di-morpholin-4-yl-2-phenyl-4-thiophen-2-yl-3,4-dihydro-pyrimido[4,5-d]pyridazine 
• 1081-34-1 2,2':5',2''-terthiophene 

Relevant academic research and scientific papers

Cocondensation reactions of heterocyclic aromatic compounds with lithium, calcium and magnesium atoms at 77 K

Calcium and magnesium atoms were cocondensed with aromatic heterocycles containing five- and six-membered rings in the presence of THF at 77 K. In the case of calcium the cocondensation with five-membered heterocyclic compounds resulted in C-H bond activations and led to the corresponding aryl calcium compounds, while magnesium did not show comparable reactions. When six-membered heterocyclic compounds, e.g., pyridine and 4-methylpyridine (4-picoline) were cocondensed with calcium, magnesium and lithium atoms, all reactions led to the formation of non-metallated aromatic products and the formation of metal hydride. DFT calculations at the B3LYP/6-31G** level of theory were carried out in order to interpret the pathways of the cocondensation reactions using calcium atoms and identify the possible intermediates involved. In all reactions π- and σ-complexes between calcium atoms and the heterocyclic aromatic reactant were found as stable intermediates on the energy hypersurface.

Cocondensation reactions of five-membered heterocycles with lithium atoms at 77 K

Lithium atoms were cocondensed with eight aromatic five-membered heterocycles in the presence of THF at 77 K. In the case of the oxygen- and sulfur-containing heterocycles (furans and thiophenes), the reaction resulted in C-H bond activation and led to the corresponding aryllithium compound. The other heterocycles (pyrroles) failed to react with lithium atoms in the presence of THF. A special case was found when oxazole was reacted under these cocondensation conditions; here a dilithiated product was obtained. DFT (B3LYP/6-31G **) calculations were carried out in order to interpret the pathways of the reactions and the possible intermediates. For all the reactions π- and o-complexes between lithium clusters and the heterocycles were found as stable intermediates. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Electrophilic 2-thienylselenenylation of thiophene. Preparation of oligo(seleno-2,5-thienylenes)

The substitution reactions of thiophene and 2-methylthiophene with the electrophilic selenenylating agent produced from the 2,2'-dithienyl diselenide by oxidation with iodobenzene diacetate involve only the α- positions and give rise to the formation of oligo(seleno-2,5-thienylenes). Products deriving from the attack at the α-positions of thiophene and 2- methylthiophene were also observed starting from the 5,5'-dimethyl-2,2'- dithienyl diselenide. The same electrophilic reagents reacted with furan and 2-methylfuran to afford a mixture of the mono- and di-substituted compounds. (C) 2000 Elsevier Science Ltd.

Thiophenylazobenzene: An Alternative Photoisomerization Controlled by Lone-Pair???π Interaction

Azoheteroarene photoswitches have attracted attention due to their unique properties. We present the stationary photochromism and ultrafast photoisomerization mechanism of thiophenylazobenzene (TphAB). It demonstrates impressive fatigue resistance and photoisomerization efficiency, and shows favorably separated (E)- and (Z)-isomer absorption bands, allowing for highly selective photoconversion. The (Z)-isomer of TphAB adopts an unusual orthogonal geometry where the thiophenyl group is perfectly perpendicular to the phenyl group. This geometry is stabilized by a rare lone-pair???π interaction between the S atom and the phenyl group. The photoisomerization of TphAB occurs on the sub-ps to ps timescale and is governed by this interaction. Therefore, the adoption and disruption of the orthogonal geometry requires significant movement along the inversion reaction coordinates (CNN and NNC angles). Our results establish TphAB as an excellent photoswitch with versatile properties that expand the application possibilities of AB derivatives.

Rhodium-Catalyzed Intermolecular Silylation of Csp?H by Silacyclobutanes

The signature reactivity of silacyclobutane (SCB) is their cycloaddition reactions with various π bonds. Recently, the first cases were disclosed where SCBs reacted with both Csp2?H and Csp3?H σ bonds in an intramolecular fashion. Herein, it is reported that SCB is also an efficient reagent for Csp?H bond silylation. Thus, rhodium-catalyzed intermolecular reactions between SCBs and terminal alkynes produced a series of symmetrical and unsymmetrical tetraorganosilicons bearing a Csp?Si functionality. Preliminary studies suggested that the reaction did not involve a cycloaddition pathway, but instead a direct activation of Csp?H bonds.

Synthesis of Benzosiloles by Intramolecular anti-Hydroarylation via ortho-C-H Activation of Aryloxyethynyl Silanes

Straightforward synthesis of benzosiloles was achieved by the invention of Pd/acid-catalyzed intramolecular anti-hydroarylation of aryloxyethynyl(aryl)silanes via ortho-C-H bond activation. The aryloxy group bound to the ethynyl carbon is the key factor for this transformation.

LIPIDIC FURAN, PYRROLE, AND THIOPHENE COMPOUNDS FOR USE IN THE TREATMENT OF ATROPHIC VAGINITIS

Provided herein are lipidic furan, pyrrole, and thiophene compounds, compositions, and methods using such compounds and compositions for the treatment of atrophic vaginitis. Specifically, the invention includes administering an effective amount of a compound of Formula I, I′, or I″, or a pharmaceutically acceptable composition, salt, isotopic analog, prodrug, or combination thereof, to a subject suffering from atrophic vaginitis.

Chemoselective Ketone Synthesis by the Addition of Organometallics to N-Acylazetidines

A general and highly chemoselective method for the synthesis of ketones by the addition of organometallics to N-acylazetidines via stable tetrahedral intermediates is reported for the first time. The transformation is characterized by its wide substrate scope and exquisite selectivity for the ketone products even when a large excess of nucleophilic reagents is used. Even of broader interest is the use of N-acylazetidines as bench-stable, readily available amide acylating reagents, in which the reactivity is controlled by amide pyramidalization and strain of the four-membered ring to afford synthetically valuable building blocks.

Is carbon dioxide able to activate halogen/lithium exchange?

The unexpected effect of carbon dioxide on halogen-lithium exchange (HLE) reactions of selected haloarenes with tBuLi was investigated. In an aliphatic hydrocarbon solvent (pentane), the HLE does not occur at ca. -70 C but, surprisingly, pouring the mixture of reactants onto dry ice and subsequent aqueous acidic hydrolysis gave carboxylic acids resulting from the quench of the first-formed aryllithiums with carbon dioxide. This suggests that CO 2 acts as a promoter of the HLE and, subsequently, serves as an electrophile to trap the aryllithium intermediates that are generated in situ. Theoretical DFT calculations were used to develop a plausible mechanism for the reaction, which indicates that CO2 is a much weaker donor than tetrahydrofuran (THF) so the cleavage of inert tBuLi cubic tetramers into more reactive solvated dimeric species (tBuLi)2(CO2) 4 is disfavored by 42.8 kJ per mol of (tBuLi)4. It is possible that this deaggregation process occurs to some extent when a large excess of CO2 is used. Copyright

Synthetic routes to fluorescent dyes exhibiting large stokes shifts

Derivatives of isomeric 2-(hydroxytolyl)-4,6-dimethylamino-1,3,5-triazines have been synthesized in high yields in a controlled manner using a multistep reaction sequence. Iodination of either 2-(1′-hydroxy-6′-methylphen- 2′-yl)- or 2-(1′-hydroxy-4′-methylphen-2′-yl)-4,6- dimethylamino-1,3,5-triazine with ICl provides species differing in the positioning of the iodo group relative to the hydroxyl which readily undergo Suzuki, Sonogashira, and Heck reactions under Pd(0) catalysis. Thus, thienyl, bisthienyl, and 3,4-ethylenedioxythienyl groups have been directly grafted, while unsubstituted polycyclic aromatics such as pyrene and perylene have been linked via alkyne bridges, as have ethynyldifluoroborondipyrromethane (BODIPY) dyes prepared in situ. The presence of a hydrogen bond in the ground state involving the hydroxyl substituent has been established by proton NMR and several X-ray structure determinations. All of the new dyes with a simple substituent (phenyl, thienyl) exhibited a pronounced green fluorescence resulting from an intramolecular proton transfer in the excited state (ESIPT) which produces a large Stokes shift (>10 000 cm-1). With other dyes, the fluorescence of the keto form responsible for the ESIPT process could be used as the input energy in efficient intramolecular energy transfer processes. Replacing perylene with pyrene allowed reversal of the direction of energy transfer from the polyaromatic module to the keto form.