Denmark Scott E, Matesich Zachery D
Roger Adams Laboratory, Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
J Org Chem. 2014 Jul 3;79(13):5970-86. doi: 10.1021/jo501004j. Epub 2014 Jun 13.
The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO2-t-Bu, COMe, Ph, CH(OEt)2, and Me) undergo high-yielding additions with aromatic, α,β-unsaturated, and aliphatic aldehydes. The conditions of the reaction were found to be mild (75 °C, 24-48 h) and only required the use of 2-3 mol % of the triruthenium dodecacarbonyl catalyst under 40-80 psi of CO. The stoichiometries of water and allylic acetate employed were found to be critical to reaction efficiency.
钌催化的醛与烯丙基乙酸酯的烯丙基化反应已得到扩展，能够在烯丙基组分的2-位引入取代基。带有各种取代基（叔丁基碳酸酯、乙酰基、苯基、二乙氧基甲基和甲基）的烯丙基乙酸酯能与芳香醛、α,β-不饱和醛和脂肪醛进行高产率的加成反应。该反应条件温和（75 °C，24 - 48小时），仅需在40 - 80 psi的一氧化碳压力下使用2 - 3 mol%的十二羰基三钌催化剂。发现所用水和烯丙基乙酸酯的化学计量比对于反应效率至关重要。
