79048-33-2

Upstream product

• 813-19-4 bis(tri-n-butyltin) 
• 99-90-1 para-bromoacetophenone 
• 1067-52-3 tributyltin methoxide 
• 99-91-2 para-chloroacetophenone 
• 1461-22-9 tributyltin chloride 
• 4360-68-3 2-(4-bromophenyl)-2-methyl-1,3-dioxolane 
• 13329-40-3 4-Iodoacetophenone 

Downstream Products

• 859233-91-3 3-acetoxy-(17α,20Z)-21-[(4-acetyl)phenyl]-19-norpregna-1,3,5(10),20-tetraene-17β-ol 
• 92-91-1 biphenyl-4-acetaldehyde 
• 787-69-9 4,4'-diacetylbiphenyl 
• 403-42-9 1-(4-fluorophenyl)ethanone 

Relevant academic research and scientific papers

Method for converting substituted sodium aryl sulfonate to aryl tri-n-butyltin

The invention discloses a method for converting substituted sodium acryl sulfonate to aryl tri-n-butyltin. The synthetic method of the aryl tri-n-butyltin compound comprises the following steps: uniformly mixing sodium aryl sulfonate, silver carbonate, bis(tri-tert-butylphosphine)palladium, and hexabutyldistannane in a solvent, reacting for 1 to 8 hours at 80 to 140 DEG C, and after the reaction is ended, concentrating; and performing the column chromatography, and obtaining a pure aryl tri-n-butyltin product. The adopted raw material is sodium aryl sulfonate which is significant in supplementation, wide in source, cheap and easy to obtain compared with the existing method adopting aromatic halides as a raw material. The reaction in the invention has good tolerance and universality for a functional group, and the substituent group can be hydrogen, methyl, tertiary butyl, fluorine, chlorine, bromine, cyanogroup, trifluoromethyl, nitro, acetyl or carbethoxy.

Synthesis of arylstannanes by palladium-catalyzed desulfitative coupling reaction of sodium arylsulfinates with distannanes

A novel Pd-catalyzed desulfitative cross-coupling reaction of sodium arylsulfinates with hexaalkyl distannanes is realized, allowing the facile synthesis of functionalized arylstannanes with moderate to excellent yields. The successful implement of gram-scale synthesis and tandem Stille coupling reaction demonstrates the potential applications of this method in organic synthesis.

Stannylation of Aryl Halides, Stille Cross-Coupling, and One-Pot, Two-Step Stannylation/Stille Cross-Coupling Reactions under Solvent-Free Conditions

Solvent-free protocols for palladium-catalyzed stannylation of aryl halides, Stille cross-coupling, and one-pot, two-step stannylation/Stille cross-coupling (SSC) are reported for the first time. (Het)aryl halides bearing acceptor, donor, as well as sterically demanding substituents are stannylated and/or coupled in high yields. The reactions are catalyzed by conventional palladium(II) acetate/PCy3 [Pd(OAc)2/PCy3] under air, using available base CsF, and without the use of high purity reagents. The developed synthetic procedures are versatile, robust, and easily scalable. The absence of solvent, and the elimination of isolation procedures of aryl stannanes makes the SSC protocol simple, step economical, and highly efficient for the synthesis of biaryls in a one-pot two-step procedure.

Copper(II)-Mediated [11C]Cyanation of Arylboronic Acids and Arylstannanes

A copper-mediated method for the transformation of diverse arylboron compounds and arylstannanes to aryl-[11C]-nitriles is reported. This method is operationally simple, uses commercially available reagents, and is compatible with a wide variety of substituted aryl- and heteroaryl substrates. This method is applied to the automated synthesis of high specific activity [11C]perampanel in 10% nondecay-corrected radiochemical yield (RCY).

Copper-Mediated Radiofluorination of Arylstannanes with [18F]KF

A copper-mediated nucleophilic radiofluorination of aryl- and vinylstannanes with [18F]KF is described. This method is fast, uses commercially available reagents, and is compatible with both electron-rich and electron-deficient arene substrates. This method has been applied to the manual synthesis of a variety of clinically relevant radiotracers including protected [18F]F-phenylalanine and [18F]F-DOPA. In addition, an automated synthesis of [18F]MPPF is demonstrated that delivers a clinically validated dose of 200 ± 20 mCi with a high specific activity of 2400 ± 900 Ci/mmol.

A Sn atom-economical approach toward arylstannanes: Ni-catalysed stannylation of aryl halides using Bu3SnOMe

Stannylation of carbon-halogen bonds is one of the most promising and straightforward approaches for the preparation of organostannane compounds. Although a wide variety of methods are now available, all protocols require the use of highly nucleophilic organometals or wasteful stannyl sources like distannanes. Here, we report a new nickel-catalysed stannylation of aryl and alkenyl-halides using Bu3SnOMe as a stannyl source to afford aryl and vinyl-stannanes, respectively. This method enables the stannylation of not only bromides, but also chlorides and triflates to furnish functionalized aryl- and alkenyl-stannanes without the release of wasteful and toxic stannyl byproducts.

Application of a promiscuous Arthrobacter sp. from Antarctic in aerobic (R)-selective deracemization and anaerobic (S)-selective reduction

Inspired by enzyme-catalyzed reactions with microorganisms found in harsh marine environments, in which the amount of oxygen is restrict, we have shown that Arthrobacter sp. can perform different chemical transformations by switching from anaerobic to aerobic reaction conditions. Depending on the presence or absence of oxygen, either alcohol deracemization or ketone reduction with enantiocomplementary selectivities can be performed by the same microorganism. For example, reactions performed in the presence of oxygen favored the deracemization process, in which a racemic mixture of 1-(4-methylphenyl)ethanol was enriched to the (R)-alcohol in high conversion (94%) and high enantiomeric excess (94%). On the other hand, reaction in the absence of oxygen favored the reduction process, in which 4-methyl-acetophenone was converted to the (S)-alcohol in good conversion (58%) and excellent enantiomeric excess (>99%). These concepts were applied for both deracemization and enantioselective reduction of heteroatom-containing (silicon, phosphorus, tin and boron) molecules. Moreover, preparative scale reactions were also performed for both chemical processes.

New and simple one-step cobalt-catalyzed preparation of functionalized arylstannanes from the corresponding aryl bromides or iodides

The process for the preparation of functionalized arylstannanes from the corresponding aryl bromides or iodides was described. The corresponding arylstannane was detected by gas chromatography using an internal standard alkane. The two-step coupling react

Preparation of Arylbutyltin Having Electron-withdrawing Group by Palladium Catalyzed Reaction of Hexabutylditin with Aryl Iodide

Nitro-, acyl-, and cyanophenyltributyltin can be prepared by the reaction of hexabutylditin with the corresponding aryl iodide in the presence of a catalytic amount of tetrakis(triphenylphosphine)palladium.

SYNTHESIS OF ORGANOTRIALKYLSTANNANES. THE REACTION BETWEEN ORGANIC HALIDES AND HEXAALKYLDISTANNANES IN THE PRESENCE OF PALLADIUM COMPLEXES

The aryl halides YC6H4X (X=Br or I) have been shown to react with the distannanes (R3Sn)2 (R=n-Bu or Me) in toluene in the presence of or to give the compounds YC6H4SnR3 for (a) R=n-Bu, Y=H, p-OMe, o-Me, p-Me, m-Cl, p-Cl, m-CN, p-COCH3 and m-NO2, and (b) R=Me, Y=H, p-OMe, p-Me, p-CN, p-COCH3, m-NO2 and p-NO2.Benzyl halides YC6H4CH2X (X=Cl or Br) similarly give YC6H4CH2SnR3 for (a) R=n-Bu, Y=H, m-OMe, p-OMe, m-Cl, m-CN, and m-NO2, and (b) R=Me, Y=m-Cl, m-CN, p-CN and m-NO2.These reactions are of special value as preparative procedures in cases in which Grignard or organolithium reagents cannot be used.Allyl chloride and bromide were likewise shown to react with (n-Bu3Sn)2 to give CH2=CHCH2SnBu3, but n-BuCl and n-BuBr gave only a trace of n-Bu4Sn.The mixed dimetallo species n-Bu3SnSiMe3 was shown to react with aryl bromides YC6H4Br (X=H, p-OMe, p-Me, or p-Cl) to give the arylsilicon compounds YC6H4SiMe3, with no aryltin products.