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

Departament de Química

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Resum

© 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.

Idioma original	Anglès
Pàgines (de-a)	12747-12750
Revista	Journal of the American Chemical Society
Volum	138
Número	39
DOIs	https://doi.org/10.1021/jacs.6b07999
Estat de la publicació	Publicada - 5 d’oct. 2016

Accés al document

10.1021/jacs.6b07999

CCDC 1508750: Experimental Crystal Structure Determination
Izquierdo, S. (Creador), Essafi, S. (Creador), Del Rosal, I. (Creador), Vidossich, P. (Creador), Pleixats, R. (Creador), Vallribera, A. (Creador), Ujaque, G. (Creador), Lledós, A. (Creador) & Shafir, A. (Creador), Cambridge Crystallographic Data Centre, 7 d’oct. 2016
DOI: 10.5517/ccdc.csd.cc1mmzcl, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mmzcl&sid=DataCite
Conjunt de dades
CCDC 1483635: Experimental Crystal Structure Determination
Guerrero, M. (Creador), Calvet, T. (Creador), Font-Bardia, M. (Creador) & Pons, J. (Creador), Cambridge Crystallographic Data Centre, 7 d’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
Conjunt de dades
CCDC 1508751: Experimental Crystal Structure Determination
Izquierdo, S. (Creador), Essafi, S. (Creador), Del Rosal, I. (Creador), Vidossich, P. (Creador), Pleixats, R. (Creador), Vallribera, A. (Creador), Ujaque, G. (Creador), Lledós, A. (Creador) & Shafir, A. (Creador), Cambridge Crystallographic Data Centre, 7 d’oct. 2016
DOI: 10.5517/ccdc.csd.cc1mmzdm, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc1mmzdm&sid=DataCite
Conjunt de dades

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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",

year = "2016",

month = oct,

day = "5",

doi = "10.1021/jacs.6b07999",

language = "English",

volume = "138",

pages = "12747--12750",

journal = "Journal of the American Chemical Society",

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publisher = "American Chemical Society",

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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

SN - 0002-7863

VL - 138

SP - 12747

EP - 12750

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 39

ER -

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

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Conjunts de dades

CCDC 1508750: Experimental Crystal Structure Determination

CCDC 1483635: Experimental Crystal Structure Determination

CCDC 1508751: Experimental Crystal Structure Determination

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