کد مقاله کد نشریه سال انتشار مقاله انگلیسی ترجمه فارسی نسخه تمام متن
6456424 1419919 2017 5 صفحه PDF سفارش دهید دانلود رایگان
عنوان انگلیسی مقاله ISI
Editor's choice paperCatalytic redox isomerization of allylic alcohols with rhodium and iridium complexes with ferrocene phosphine-thioether ligands
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موضوعات مرتبط
مهندسی و علوم پایه مهندسی شیمی کاتالیزور
پیش نمایش صفحه اول مقاله
Editor's choice paperCatalytic redox isomerization of allylic alcohols with rhodium and iridium complexes with ferrocene phosphine-thioether ligands
چکیده انگلیسی


- Full hydrogenation of allylic alcohols under 30 bar dihydrogen.
- Redox isomerization of allylic alcohols.
- Rhodium and iridium complexes with ferrocene phosphine-thioether ligands.
- Activation of rhodium diene complexes under transfer hydrogenation reaction conditions.

Complexes [M(P,SR)(diene)X] where (P,SR) = CpFe[1,2-C5H3(PPh2)(CH2SR)] (M = Ir, R = tBu or Bn diene = cod, X = Cl; M = Rh, diene = cod or nbd; X = BF4 or Cl) were used as precatalysts for the redox isomerization of various allylic alcohols (7a-e) to the corresponding saturated ketones (8a-e) and or hydrogenation to the saturated alcohol (9a-e). In optimization studies using 1-phenyl-2-propen-1-ol (7a) in THF and in iPrOH/MeONa, the only observed product was the saturated alcohol 1-phenyl-1-propanol (9a) when working under a 30 bar H2 pressure, but activation for only 1 min under H2 pressure and then continuation under 1 bar of H2 or Ar led to increasing amounts of the allylic isomerization product propiophenone (8a). Continued reaction under H2 converted (8a) into (9a). The Rh precatalysts were more active than the Ir analogues. For the rhodium precatalysts (3) and (4), the redox isomerization reaction could be carried out after precatalyst activation in iPrOH/MeONa under Ar at 82 °C (without H2) with complete conversion in 1 h (1% catalyst loading). However, longer reaction times resulted in slow transfer hydrogenation of (8a) leading to (9a) with low enantiomeric excess. Extension of the H2-free activation of the Rh precatalysts in iPrOH to other allylic alcohol substrates (7b-d) yielded the corresponding ketones with good to excellent yields and excellent chemoselectivities under appropriate conditions.

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ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Molecular Catalysis A: Chemical - Volume 426, Part B, January 2017, Pages 376-380
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