Pentafluorophenyltributylstannane synthesis

Yield:1045-56-3 98%

Reaction Conditions:

bis(1,5-cyclooctadiene)nickel ⁽⁰⁾;tris(1-methylethyl)phosphine at 80; for 3 h;Product distribution / selectivity;

Steps:

In a first example process, a single-step catalytic stannylation of a fluorinated arene compound was achieved using Bu₃Sn(CHCH₂) or Me₃Sn(CHCH₂) as a first organometallic compound in the presence of Ni(COD)₂ with at least one of MeNC₅H₄NⁱPr and PⁱPr₃ as a catalyst as follows: The preferred reaction advantageously shows quantitative functionalization and may be performed using as little as 1 mol % of Ni(COD)₂ and MeNC₅H₄NⁱPr to go to completion. Test reactions were run at room temperature and yielded ethylene as a by-product. The reaction may further be performed without addition of solvent.In test samples the above reaction has been demonstrated to work with a number of different fluorinated arene compounds yielding resulting functionalized products in excess of 90%.Table 1 below illustrates example single-step reactions of the present invention involving use of fluorinated arene compounds having 2 to 5 fluorine substituents, the catalyst Ni(COD)₂ and the ancillary ligand MeNC₅H₄NⁱPr and/or PⁱPr₃. The yield percent marked with the superscript a provides NMR yield from integration of ¹⁹F[¹H] NMR spectra, and yield percent marked with the superscript b provides isolated yield after chromatography. The condition hours marked with the superscript c and d denote that the reaction was carried out using 2.5 molar amount of Bu₃Sn(CHCH₂) and 10 fold excess of the fluorinated arene compound, respectively.

References:

US2011/282087,2011,A1 Location in patent:Page/Page column 4