Acid Activation in Phenyliodine Dicarboxylates: Direct Observation, Structures, and Implications

The use of the hypervalent iodine reagents in oxidative processes has become a staple in modern organic synthesis. Frequently, the reactivity of λ3 iodanes is further enhanced by acids (Lewis or Brønsted). The origin of such activation, however, has remained elusive. Here, we use the common combinat...

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Published inJournal of the American Chemical Society Vol. 138; no. 39; pp. 12747 - 12750
Main Authors Izquierdo, Susana, Essafi, Stéphanie, del Rosal, Iker, Vidossich, Pietro, Pleixats, Roser, Vallribera, Adelina, Ujaque, Gregori, Lledós, Agustí, Shafir, Alexandr
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 05.10.2016
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
IODIDES
CROWN-ETHER COMPLEXES
PRODUCTS
ARYLATION
CHEMISTRY
BOND FORMATION
POLYVALENT IODINE
HYPERVALENT IODINE(III) REAGENT
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Summary:The use of the hypervalent iodine reagents in oxidative processes has become a staple in modern organic synthesis. Frequently, the reactivity of λ3 iodanes is further enhanced by acids (Lewis or Brønsted). The origin of such activation, however, has remained elusive. Here, we use the common combination of PhI­(OAc)2 with BF3·Et2O as a model to fully explore this activation phenomenon. In addition to the spectroscopic assessment of the dynamic acid–base interaction, for the first time the putative PIDA·BF3 complex has been isolated and its structure determined by X-ray diffraction. Consequences of such activation are discussed from a structural and electronic (DFT) points of views, including the origins of the enhanced reactivity.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.6b07999