López-Sánchez Belén, Scalambra Franco, Cano-Asensio Judit, Romerosa Antonio
Área de Química Inorgánica-CIESOL, Universidad de Almería Almería Spain
RSC Adv. 2025 Aug 18;15(35):29023-29033. doi: 10.1039/d5ra03564c. eCollection 2025 Aug 11.
The isomerization of substituted allylic alcohols, including α-vinyl benzyl alcohol, -1,3-diphenyl-2-propen-1-ol, cinnamyl alcohol, coniferyl alcohol, 4-nitrocinnamyl alcohol, farnesol, 1,5-hexadien-3,4-diol, (1)-(-)-myrtenol and ,-(-)-carveol, catalyzed by the RuCp(OH)(PTA) (1) and RuCp(OH)(mPTA) (2) (PTA = 1,3,5-triaza-7-phosphaadamantane, mPTA = -methyl-1,3,5-triaza-7-phosphaadamantane) complexes was examined in pure water and water-containing media. The isomerization of the chalcone -1,3-diphenyl-2-propen-1-ol catalyzed by 1 to produce the natural product propiophenone displays the highest known turnover number for this reaction to date (TON = 200 and TOF = 40 h). A study delving into the catalytic reaction mechanisms was carried out, aiming to understand the influence of different functional groups on the studied isomerization processes. The intermediates of the isomerization of α-vinylbenzyl alcohol and 1,5-hexadien-3,4-diol catalyzed by 1 and 2 were isolated and characterized by NMR spectroscopy.
研究了在纯水和含水介质中，由RuCp(OH)(PTA) (1)和RuCp(OH)(mPTA) (2)（PTA = 1,3,5-三氮杂-7-磷杂金刚烷，mPTA = -甲基-1,3,5-三氮杂-7-磷杂金刚烷）配合物催化的取代烯丙醇的异构化反应，这些取代烯丙醇包括α-乙烯基苄醇、-1,3-二苯基-2-丙烯-1-醇、肉桂醇、松柏醇、4-硝基肉桂醇、法尼醇、1,5-己二烯-3,4-二醇、(1)-(-)-桃金娘烯醇和,-(-)-香芹醇。由1催化查耳酮-1,3-二苯基-2-丙烯-1-醇异构化生成天然产物苯丙酮的反应，是迄今为止该反应已知的最高周转数（TON = 200，TOF = 40 h）。开展了一项深入研究催化反应机理的研究，旨在了解不同官能团对所研究的异构化过程的影响。通过NMR光谱对由1和2催化的α-乙烯基苄醇和1,5-己二烯-3,4-二醇异构化的中间体进行了分离和表征。
