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

106 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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10.1021/jacs.6b07999

CCDC 1508749: Experimental Crystal Structure Determination
Izquierdo, S. (Creator), Essafi, S. (Creator), Del Rosal, I. (Creator), Vidossich, P. (Creator), Pleixats Rovira, R. (Creator), Vallribera, A. (Creator), Ujaque Perez, G. (Creator), Lledos Falco, A. (Creator) & Shafir, A. (Creator), Cambridge Crystallographic Data Centre, 7 Oct 2016
DOI: 10.5517/ccdc.csd.cc1mmzbk, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mmzbk&sid=DataCite
Dataset
CCDC 1508752: Experimental Crystal Structure Determination
Izquierdo, S. (Creator), Essafi, S. (Creator), Del Rosal, I. (Creator), Vidossich, P. (Creator), Pleixats Rovira, R. (Creator), Vallribera, A. (Creator), Ujaque Perez, G. (Creator), Lledos Falco, A. (Creator) & Shafir, A. (Creator), Cambridge Crystallographic Data Centre, 7 Oct 2016
DOI: 10.5517/ccdc.csd.cc1mmzfn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mmzfn&sid=DataCite
Dataset
CCDC 1483635: Experimental Crystal Structure Determination
Guerrero, M. (Creator), Calvet, T. (Creator), Font-Bardia, M. (Creator) & Pons Picart, J. (Creator), Cambridge Crystallographic Data Centre, 7 Oct 2016
DOI: 10.5517/ccdc.csd.cc1lsv6f, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1lsv6f&sid=DataCite
Dataset

Cite this

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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.",

author = "Susana Izquierdo and St{\'e}phanie Essafi and {Del Rosal}, Iker and Pietro Vidossich and Roser Pleixats and Adelina Vallribera and Gregori Ujaque and Agust{\'i} Lled{\'o}s and Alexandr Shafir",

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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

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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

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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

Abstract

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Datasets

CCDC 1508749: Experimental Crystal Structure Determination

CCDC 1508752: Experimental Crystal Structure Determination

CCDC 1483635: Experimental Crystal Structure Determination

Cite this