Robb Kevin A, Athavale Soumitra V, Denmark Scott E
Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, IL 61801, USA.
Synlett. 2019;30(14):1656-1661. doi: 10.1055/s-0039-1690111. Epub 2019 Aug 7.
The kinetic behavior of the Lewis base-catalyzed sulfenocyclization of polyenes in hexafluoroisopropyl alcohol (HFIP) was explored. The rate of reaction is not dependent on the electronic properties of the terminal nucleophile, suggesting that this capture step is not rate limiting. Additionally, fractional orders were observed for two of the reaction components. This intriguing profile appears unique to the polyene sulfenocyclization reaction and is not merely due to solvent effects.
研究了在六氟异丙醇（HFIP）中Lewis碱催化的多烯硫代环化反应的动力学行为。反应速率不依赖于末端亲核试剂的电子性质，这表明该捕获步骤不是速率决定步骤。此外，观察到两种反应组分呈现分数级反应级数。这种有趣的反应特征似乎是多烯硫代环化反应所特有的，而不仅仅是由溶剂效应导致的。
