Synthesis and functionalization of (Z)-1,2-difluoro-1-tri-n-butylstannyl-1,4-pentadiene

•Coupling 2 with substituted aryl iodides/P(PPh3)4/Cu(I)I gave the arylated products.•Coupling 2 with vinyl iodides stereospecifically gave the trienyl products.•Hydroboration/oxidation of 2 gave the corresponding (Z)-HOCH2CH2CH2CFCFSn(n-Bu)3.•Coupling 11 with substituted aryl halides gave the difunctionalized olefin.

The Zn reagent prepared from (E)-1,2-difluoro-1-iodo-2-triethylsilylethene followed by reaction with allyl bromide gave (Z)-1,2-difluoro-1-triethylsilyl-1,4-pentadiene. Further reaction of (Z)-1,2-difluoro-1-triethylsilyl-1,4-pentadiene with KF, n-Bu3SnCl, in DMF at 70 °C gave (Z)-1,2-difluoro-1-tri-n-butylstannyl-1,4-pentadiene. Coupling of (Z)-1,2-difluoro-1-tri-n-butylstannyl-1,4-pentadiene with substituted aryl iodides under Stille–Libeskind (Pd(PPh3)4/Cu(I)I) conditions gave the arylated product. Similar coupling of perfluorovinyl iodides stereospecifically gave the corresponding trienes. Hydroboration/oxidation with 9-BBN and H2O2 of (Z)-1,2-difluoro-1-tri-n-butylstannyl-1,4-pentadiene gave (Z)-4,5-difluoro-5-tri-n-butylstannyl-4-penten-1-ol. Additional couplings of (Z)-4,5-difluoro-5-tri-n-butylstannyl-4-penten-1-ol with substituted aryl iodides under Stille–Libeskind conditions gave the corresponding difunctionalized molecule.

Graphical abstract(Z)-H2CCHCH2CFCFSiEt3 can be readily prepared from the zinc reagent of (E)-IFCCFSiEt3, Cu(I)Br, and allyl bromide. When (Z)-H2CCHCH2CFCFSiEt3 was treated with KF, n-Bu3SnCl, in DMF at 70 °C, (Z)-H2CCHCH2CFCFSn(n-Bu)3 was isolated in good yield (81%). Coupling of (Z)-H2CCHCH2CFCFSn(n-Bu)3 with substituted aryl iodides and perfluorovinyl iodides under Stille–Libeskind (Pd(PPh3)4/Cu(I)I) condition stereospecifically gave (E)-CH2CHCH2CFCFAr and (E,E)-CH2CHCH2CFCFCFCFCF3. Hydroboration with 9-BBN and oxidation with H2O2/NaOH of (Z)-H2CCHCH2CFCFSn(n-Bu)3 gave (Z)-HOCH2CH2CH2CFCFSn(n-Bu)3 which can be further coupled with substituted aryl iodides under Stille–Libeskind conditions to give (E)-HOCH2CH2CH2CFCFAr.Figure optionsDownload full-size imageDownload as PowerPoint slide