Reactivity of mixed organozinc and mixed organocopper reagents: 11. Nickel-catalyzed atom-economic aryl-allyl coupling of mixed (n-alkyl)(aryl)zincs

KALKAN M.

APPLIED ORGANOMETALLIC CHEMISTRY, cilt.28, sa.9, ss.725-732, 2014 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 28 Sayı: 9
  • Basım Tarihi: 2014
  • Doi Numarası: 10.1002/aoc.3192
  • Dergi Adı: APPLIED ORGANOMETALLIC CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.725-732
  • Anahtar Kelimeler: alkylarylzincs, mixed diorganozincs, allylation, Ni catalyst, CONJUGATE MICHAEL-ADDITIONS, ORGANIC GROUP-TRANSFER, ENANTIOSELECTIVE SYNTHESIS, DIORGANOZINC COMPOUNDS, ASYMMETRIC-SYNTHESIS, SECONDARY, CHEMISTRY, ALCOHOLS, SUBSTITUTION, ALKYLATION
  • Ankara Üniversitesi Adresli: Evet

Özet

Group selectivity in the allylation of mixed (n-butyl)(phenyl) zinc reagent can be controlled by changing reaction parameters. CuCN-catalyzed allylation in tetrahydrofuran (THF)-hexamethylphosphoric triamide is n-butyl selective and also gamma-selective in the presence of MgCl2, whereas CuI-catalyzed allylation in THF in the presence of n-Bu3P takes place with a n-butyl transfer:phenyl transfer ratio of 23:77 and an alpha:gamma transfer ratio of phenyl of 76:24. NiCl2(Ph3P)(2)-catalyzed allylation in the presence of LiCl is phenyl selective with an alpha:gamma ratio of 65:35. The reaction of methyl-or n-butyl(aryl) zinc reagents with an allylic electrophile in THF at room temperature in the presence of NiCl2(Ph3P)(2) catalyst and LiCl as an additive provides an atom-economic alternative to aryl-allyl coupling using diarylzincs. Copyright (C) 2014 John Wiley & Sons, Ltd.