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O-Iodoxybenzoic acid and related iodoxyarenes. Edmund William Dwerryhouse Burke Wednesday 23 rd February 2011. History. Discovered in at the end of the 19 th century Biologically tested and used as a medicine Not really used until the end of the 20 th. Structure and bonding.

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o iodoxybenzoic acid and related iodoxyarenes

O-Iodoxybenzoic acid and related iodoxyarenes

Edmund William Dwerryhouse Burke

Wednesday 23rd February 2011

history
History
  • Discovered in at the end of the 19th century
  • Biologically tested and used as a medicine
  • Not really used until the end of the 20th
structure and bonding
Structure and bonding
  • O-iodoxybenzoic acid (IBX), exists in a single tautomeric form, IUPAC name;1-hydroxy-1-oxo-1H-1l5-benzo[d][1,2]iodoxol-3-one
  • Planar except for O4, leading to chirality
  • Can be crystallize as a conglomerate
  • Octahedral geometry around iodine due to intermolecular I-O interactions

S. F. Kirsch and A. Duschek, Angew. Chem. Int. Ed. 2011, 50, 1524 – 1552

more bonding
More bonding
  • Hypervalent bonding
    • Hypervalent atom may have colinear single bonds
    • Two types of single bond from the same atom
    • Doubly occupied p-orbitals
    • Oxo ligand is associate via a dative bond

J. I. Musher, Angew. Chem. Internat. Edit. Vol. 8 (1969), 54-68

S. F. Kirsch and A. Duschek, Angew. Chem. Int. Ed. 2011, 50, 1524 – 1552

preparation
Preparation
  • Numerous methods have been reported, either via oxidation of 2-iodosobenzoic acid or 2-iodobenzoic acid. Method of choice is now:

Marco Frigerio, Marco Santagostino, and Simona Sputore, J. Org. Chem. 1999, 64, 4537-4538

advantages of ibx and its derivatives
Advantages of IBX and its derivatives
  • Environmentally safe
  • Stable in presence of water and oxygen
  • Can be regenerated
  • Compatible with a wide range of common protecting groups
  • Does not over oxidise aldehydes to acids
  • Does not oxidise tertiary amines or heterocycles
disadvantages of ibx and its derivatives
Disadvantages of IBX and its derivatives
  • Lack of solubility in most organic solvents
  • Explosive

Overcome by

  • Polymer bound IBX
  • Use of SIBX, formulation of benzoic acid, 2-iodobenzoic acid, and IBX
  • Derivatives

Marcel M¸lbaier and Athanassios Giannis, Angew. Chem. Int. Ed. 2001, 40, 4393-4394

mechanism
Mechanism

Hypervalent twist mechanism

S. F. Kirsch and A. Duschek, Angew. Chem. Int. Ed. 2011, 50, 1524 – 1552

in situ generation of ibx
In situ generation of IBX

C. Bulman Page, L. F. Appleby, B. R. Buckley, S. M. Allin, M. J. McKenzieb, Synlett 2007, No. 10, 1565–1568

some derivatives
Some Derivatives

Jarugu Narasimha Moorthy, Nidhi Singhal and Kalyan Senapati, Tetrahedron Lett. 49 (2008) 80–84

S. F. Kirsch and A. Duschek, Angew. Chem. Int. Ed. 2011, 50, 1524 – 1552

example use of a derivative
Example use of a derivative

2 eq.

DCM, rt. 1h

87 %

Paul A. Grieco,' Jon L. Collins,* Eric D. Moher Thomas J. Fleck, and Raymond S. Gross, J. Am. Chem. SOC. 1993, 115, 6078-6093

slide13
Some examples using

Me-IBX

Jarugu Narasimha Moorthy, Nidhi Singhal and Kalyan Senapati, Tetrahedron Lett. 49 (2008) 80–84

sulphides to sulphoxides
Sulphides to sulphoxides

Jarugu Narasimha Moorthy, Nidhi Singhal and Kalyan Senapati, Tetrahedron Lett. 49 (2008) 80–84

ibx and diols
IBX and Diols

Also make hemiaminals, then lactams

one pot reactions
One pot reactions

Fredy Leon, Daniel G. Rivera, and Ludger A. Wessjohann, J. Org. Chem., 73, 2008, 1762-1767

dehydrogenation with ibx
Dehydrogenation with IBX

Aromatization

Dehydrogenation of carbonyls

slide19

K. C. Nicolaou, T. Montagnon, P. S. Baran, and Y.-L. Zhong, J. Am. Chem. Soc.,124, 2002, 2245-2258

dearomatization of phenols
Dearomatization of Phenols

Derek Magdziak, Andy A. Rodriguez, Ryan W. Van De Water, and Thomas R. R. Pettus, Org. Lett., 4, 2002, 285-288

summary
Summary
  • Broad array of reactions
  • Various reaction mechanisms
  • Mild and selective oxidising agents
  • Easy to use