TY - JOUR
T1 - Acid Activation in Phenyliodine Dicarboxylates: Direct Observation, Structures, and Implications
AU - Izquierdo, Susana
AU - Essafi, Stéphanie
AU - Del Rosal, Iker
AU - Vidossich, Pietro
AU - Pleixats, Roser
AU - Vallribera, Adelina
AU - Ujaque, Gregori
AU - Lledós, Agustí
AU - Shafir, Alexandr
PY - 2016/10/5
Y1 - 2016/10/5
N2 - © 2016 American Chemical Society. 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.
AB - © 2016 American Chemical Society. 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.
U2 - 10.1021/jacs.6b07999
DO - 10.1021/jacs.6b07999
M3 - Article
VL - 138
SP - 12747
EP - 12750
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 39
ER -