53844-49-8

Upstream product

• 3172-56-3 3,3'-bithiophene 

Downstream Products

• 26554-55-2 4,4'-dibromo-2,2'-diformyl-3,3'-bithienyl 
• 23044-17-9 2,4,2',4'-tetrabromo[3,3']bithiophenyl 
• 26518-20-7 4,4'-dibromo-2-carboxy-2'-hydroxymethyl-3,3'-bithienyl 

Relevant academic research and scientific papers

3,3′-Bithiophene-Based Chiral Bisphosphine Oxides as Organocatalysts in Silicon-Derived Lewis Acid Mediated Reactions

This account summarizes the development of new biheteroaromatic chiral bisphosphine oxides. 3,3′-Bithiophene-based phosphine oxides (BITIOPOs) have been successfully used as organocatalysts to promote Lewis base catalyzed, Lewis acid mediated stereoselective transformations. These highly electron-rich compounds, in combination with trichorosilyl derivatives (allyltrichlorosilane and silicon tetrachloride), generate hypervalent silicon species that act as chiral Lewis acids in highly diastereo- and enantioselective organic reactions. Several relevant examples related to these applications are discussed in detail. 1 Introduction 2 The BITIOPO Family 3 Enantioselective Opening of Epoxides 4 Enantioselective Allylation of Aldehydes 5 Stereoselective Direct (Double) Aldol-Type Reaction with Ketones 6 Stereoselective Direct Aldol-Type Reaction with Ester Derivatives 7 Conclusions.

TetraPh-Tol-BITIOPO: A new atropisomeric 3,3′-bithiophene based phosphine oxide as an organocatalyst in Lewis base-catalyzed Lewis acid mediated reactions

A new chiral phosphine oxide based on a 3,3′-bithiophene scaffold (TetraPh-Tol-BITIOPO) was synthesized, fully characterized and separated into antipodes through chiral HPLC. This new compound was successfully employed as an organocatalyst in Lewis base-catalyzed Lewis acid mediated reactions involving trichlorosilyl compounds. The new atropisomeric catalyst was able to promote the allylation of aldehydes with allyltrichlorosilane in up to 98% yield and up to 96% enantiomeric excess (ee), and the direct aldol reaction to afford β-hydroxy ketones and β-hydroxy thioesters, with good chemical yields and modest stereochemical efficiency. Computational studies helped to elucidate and to rationalize the stereochemical outcome of the reactions catalyzed by TetraPh-Tol-BITIOPO that was found to favour the formation of the isomer with an opposite absolute configuration in comparison with the products obtained with the previously reported 3,3′-bithiophene-based catalyst.

Inherently Chiral Spider-Like Oligothiophenes

The racemate of an inherently chiral “spider-like” octathiophene monomer T83, in which chirality is generated by torsion in its backbone, was synthesized. The racemate was resolved into configurationally stable antipodes by HPLC on a chiral stationary phase. Electrooxidation of the enantiomers resulted in materials displaying high enantiorecognition ability towards the antipodes of some chiral probes. Moreover, the T83racemate demonstrated great aptitude to stimulate formation of 3D rigid architectures if used as a cross-linking monomer for molecular imprinting. This feature was exploited to devise a molecularly imprinted polymer-based chemosensor selective for a thymine–adenine oligonucleotide.

Discrimination of Axial and Central Stereogenic Elements in Chiral Bis(oxazolines) Based on Atropisomeric 3,3′-Bithiophene Scaffolds Through Chiroptical Spectroscopies

Two diastereoisomeric pairs of bis-oxazolines, provided with a stereogenic center at carbon 4 and based on the 3,3′-bithiophene atropisomeric scaffold, were synthesized and structurally characterized. They differ in the substituents at positions 2 and 5 of the thiophene rings, which are functionalized with methyl (1) or phenyl (2) groups, respectively. In vibrational circular dichroism (VCD) spectra, recorded in CCl4solutions, it is possible to distinctly recognize the characteristic features of axial and central stereogenic elements. In tandem with Density Functional Theory (DFT) calculations, the absolute configuration (AC) of the diastereoisomers was safely established. In this case, VCD was shown to be superior to ECD (electronic circular dichroism) in the assignment of AC. The normal modes, evaluated from DFT calculations, show that the VCD signals in correspondence with the stereogenic axis of the bithiophene unit are different for 1 and 2. The VCD spectra of a molecular analog of 1, the (S)-2,2′,5,5′-tetramethyl-4,4′-bis-(diphenylphosphino)-3,3′-bithiophene oxide (3), characterized by the same 3,3′-bithiophene scaffold, but devoid of stereogenic centers, exhibits signals similar to those observed in the case of diastereoisomer (aS,R,R)-1a, associated with almost identical normal modes. Chirality 28:686–695, 2016.

Enatioselective Chalcogeno-Baylis-Hillman reaction of arylaldehydes with MVK and acrylates catalyzed by chiral thiepin-TiCl4 complex

In a rational chiral molecular design of chalcogenides, optically active thiepin with C2-symmetric chirality was synthesized from commercially available thiophene. Then enatioselective Chalcogeno-Baylis-Hillman reactions of arylaldehydes with methyl vinyl ketone (MVK) and acrylates were investigated in the presence of thiepin-Lewis acid complex. Finally, up to 64% ee was achieved in the presence of 0.2 equiv. of (S)-thiepin at 20°C. Enatioselective Chalcogeno-Baylis-Hillman reactions between benzaldehydes and acrylates were investigated in the presence of chiral thiepin-Lewis acid complex. Finally, up to 64% ee was achieved in the presence of 0.2 equiv. of (S)-thiepin at 20°C. Copyright