A pseudo‐benziodoxazine structure with intramolecular secondary I⋅⋅⋅O bonding, as shown by X‐ray analysis, is seen in a series of N‐(2‐iodylphenyl)acylamides prepared from 2‐iodoaniline (see scheme). These compounds contain a six‐membered pseudocyclic scaffold about an iodine(V) center and are able to oxidize either alcohols or sulfides, with the reactivity depending largely on the substitution pattern on the amide group adjacent to the iodyl moiety.
A simple three-step preparation of polymer-supported N-(2-iodyl-phenyl)-acylamide (NIPA resin) starting from 2-iodoaniline is described. The resin was obtained with good loading levels (0.7-0.8 mmol g(-1)) and has been successfully used for efficient oxidation of a diverse collection of alcohols. Thus, treating alcohols with 1.0 equiv of the resin in 1,2-dichloroethane under reflux for 30-60 min allowed rapid and in most cases complete conversion to the corresponding carbonyl compound.
Scaffold. -The pseudobenziodoxazine scaffold is shown to be a promising lead structure for the development of novel, selective hypervalent iodine containing oxidants [cf. (I)-(IV)]. Best results are obtained with derivative (Ie). -(LADZIATA, U.; KOPOSOV, A. Y.; LO, K. Y.; WILLGING, J.; NEMYKIN*, V. N.; ZHDANKIN, V. V.; Angew. Chem., Int. Ed. 44 (2005) 43, 7127-7131; Dep. Chem., Univ. Minn., Duluth, MN 55812, USA; Eng.) -Nuesgen 09-047
Eine Pseudo‐Benziodoxazin‐Struktur mit intramolekularer sekundärer I⋅⋅⋅O‐Bindung (siehe Schema und Strukturbild) zeichnet eine Reihe von N‐(2‐Iodylphenyl)acylamiden aus, die ausgehend von 2‐Iodanilin erhalten wurden. Je nach dem Substitutionsmuster an der benachbarten Amidgruppe oxidiert das Iod(V)‐Zentrum des sechsgliedrigen Pseudocyclus entweder Alkohole oder Sulfide.
Aldehydes Q 0320Facile Preparation and Reactivity of Polymer-Supported N-(2-Iodyl-phenyl)-acylamide, an Efficient Oxidizing System. -The polymer is applied in the oxidation a variety of alcohols. Aldehydes and ketones are obtained in excellent yields. -(LADZIATA, U.; WILLGING, J.; ZHDANKIN*, V. V.; Org. Lett. 8 (2006) 1, 167-170; Dep. Chem., Univ. Minn., Duluth, MN 55812, USA; Eng.) -R. Steudel 20-076
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