Brigham Conor E, Malapit Christian A, Lalloo Naish, Sanford Melanie S
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
ACS Catal. 2020 Aug 7;10(15):8315-8320. doi: 10.1021/acscatal.0c02950. Epub 2020 Jul 17.
This report describes the development of a nickel-catalyzed decarbonylative reaction for the synthesis of fluoroalkyl thioethers (RSR) from the corresponding thioesters. Readily available, inexpensive, and stable fluoroalkyl carboxylic acids (RCOH) serve as the fluoroalkyl (R) source in this transformation. Stoichiometric organometallic studies reveal that R-S bond-forming reductive elimination is a challenging step in the catalytic cycle. This led to the identification of diphenylphosphinoferrocene as the optimal ligand for this transformation. Ultimately, this method was applied to the construction of diverse fluoroalkyl thioethers (RSR), with R = both aryl and alkyl.
本报告描述了一种镍催化的脱羰反应,用于从相应的硫酯合成氟代烷基硫醚(RSR)。在该转化反应中,易于获得、价格低廉且稳定的氟代烷基羧酸(RCOH)用作氟代烷基(R)源。化学计量的有机金属研究表明,形成R-S键的还原消除是催化循环中的一个具有挑战性的步骤。这导致确定二苯基膦基二茂铁为该转化反应的最佳配体。最终,该方法被应用于构建多种氟代烷基硫醚(RSR),其中R既可以是芳基也可以是烷基。