Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85748 Garching bei München, Germany.
J Am Chem Soc. 2011 Jun 1;133(21):8138-41. doi: 10.1021/ja2026823. Epub 2011 May 9.
The catalytic activity of [CpRu(L)(2)(MeCN)]PF(6) (L = 2-diphenylphosphinopyridine with bulky groups at C-6) for anti-Markovnikov hydration of terminal alkynes to aldehydes is retained when one heterocyclic ligand L is replaced by L' = PPh(3). Equal amounts of CpRuCl(PPh(3))(2) (1) and phosphane L in acetone solution equilibrate to a mixture of 1, CpRuCl(L)(PPh(3)) (2), and CpRuCl(L)(2) (3), which acts as highly active in situ catalyst for preparative anti-Markovnikov hydration of alkynes in water-rich media (2 mol % [Ru], 60 °C, 3-18 h in 4:1 (v/v) acetone/water). Reactions were completed in <15 min at 160 °C.
[CpRu(L)(2)(MeCN)]PF(6)（L = 具有体积较大基团的 2-二苯基膦基吡啶）中 L 一个杂环配体被 L' = PPh(3)取代时，其催化末端炔烃反马氏加成水合生成醛的活性仍然保留。在丙酮溶液中，等摩尔量的 CpRuCl(PPh(3))(2)（1）和膦配体 L 平衡为 1、CpRuCl(L)(PPh(3))（2）和 CpRuCl(L)(2)（3）的混合物，该混合物在富含水的介质中作为炔烃反马氏加成的高效原位催化剂（2 mol % [Ru]，60 °C，3-18 h，在 4:1（v/v）丙酮/水中）。在 160 °C 下反应在 <15 min 内完成。
