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

Susana Izquierdo; Stéphanie Essafi; Iker Del Rosal; Pietro Vidossich; Roser Pleixats; Adelina Vallribera; Gregori Ujaque; Agustí Lledós; Alexandr Shafir

doi:10.1021/jacs.6b07999

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

Susana Izquierdo, Stéphanie Essafi, Iker Del Rosal, Pietro Vidossich, Roser Pleixats, Adelina Vallribera, Gregori Ujaque, Agustí Lledós, Alexandr Shafir

Department of Chemistry

Research output: Contribution to journal › Article › Research › peer-review

63 Citations (Scopus)

Abstract

© 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.

Original language	English
Pages (from-to)	12747-12750
Journal	Journal of the American Chemical Society
Volume	138
Issue number	39
DOIs	https://doi.org/10.1021/jacs.6b07999
Publication status	Published - 5 Oct 2016

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

abstract = "{\textcopyright} 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 Br{\o}nsted). 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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Acid Activation in Phenyliodine Dicarboxylates: Direct Observation, Structures, and Implications. / Izquierdo, Susana; Essafi, Stéphanie; Del Rosal, Iker; Vidossich, Pietro; Pleixats, Roser ; Vallribera, Adelina ; Ujaque, Gregori ; Lledós, Agustí; Shafir, Alexandr.

In: Journal of the American Chemical Society, Vol. 138, No. 39, 05.10.2016, p. 12747-12750.

Research output: Contribution to journal › Article › Research › peer-review

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.

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DO - 10.1021/jacs.6b07999

M3 - Article

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JF - Journal of the American Chemical Society

SN - 0002-7863

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