TY - JOUR A1 - Lee, Zachary A1 - Jones, Brandon R. A1 - Nkengbeza, Nyochembeng A1 - Phillips, Michael A1 - Valentine, Kayla A1 - Stewart, Alexis A1 - Sellers, Brandon A1 - Shuber, Nicholas A1 - Aiken, Karelle S. T1 - Iodine-mediated hydration of alkynes on keto-functionalized scaffolds: mechanistic insight and the regiospecific hydration of internal alkynes JF - Beilstein Journal of Organic Chemistry PY - 2019/// VL - 15 SP - 2747 EP - 2752 SN - 1860-5397 DO - 10.3762/bjoc.15.265 PB - Beilstein-Institut JA - Beilstein J. Org. Chem. UR - https://doi.org/10.3762/bjoc.15.265 KW - α-iodo intermediate KW - internal alkyne KW - iodine-mediated hydration KW - neighboring group participation KW - regiospecific hydration N2 - An iodine-mediated hydration reaction of alkynes serves as a green alternative to metal-catalyzed procedures. Previous work has shown that this method works well with terminal alkynes on keto-functionalized scaffolds, including 1,3-dicarbonyls and their heteroatom analogues. It was hypothesized that the reaction proceeds through a 5-exo-dig neighboring group participation (NGP) cyclization and an α-iodo intermediate. The work described herein probes the existence of the intermediate through NMR investigations and explores the scope of the hydration process with internal alkynes. The NMR experiments confirm the existence of the α-iodo intermediate, and methodology studies demonstrate that alkyl-capped, asymmetric, internal alkynes undergo a regiospecific hydration, also via the 5-exo-dig NGP pathway. ER -