Abstract
Structurally related to iodosylbenzene PhI=O, iodonium imidesPhI=NR, off-white to
pale yellow solids of low solubility, belongto the class of hypervalent iodine(III)
reagents and were first preparednearly thirty years ago. Two additional decades were
needed beforethey could be considered as useful nitrene precursors with the discoveryof
the copper-catalyzed aziridination of olefins. Since then, iminoiodaneshave been successfully
applied in the total synthesis of naturaland/or biologically active compounds. Recent
developmentsaimed at circumventing their tedious preparation led to the discoveryof
one-pot nitrogen transfers from sulfonamides, sulfamates, orcarbamates mediated by
iodosylbenzene(diacetate) PhI(OAc)2 oriodosylbenzene. Reliable functionalizations of alkanes and alkenesvia C-H insertion
or aziridination using copper or rhodiumcatalysts can now be considered as synthetically
useful processes.
-
1 Introduction
-
2 Iminoiodanes
-
2.1 General Properties
-
2.2 Methods of Preparation
-
2.3 Types of N-SubstitutedIminoiodanes
-
3 Iminoiodanes in Organic Synthesis
-
3.1 Natural Product Synthesis
-
3.2 Synthesis of Biologically Active Compounds
-
4 Recent Developments: Iodonium Ylides as in situ
Intermediates
-
4.1 Metalloporphyrin-Mediated Nitrogen Atom Transfer
-
4.2 Rhodium-Catalyzed Nitrogen Atom Transfer
-
4.3 Copper-Catalyzed Nitrogen Atom Transfer
-
5 Conclusion and Future Prospects
Key words
hypervalent iodine - iminoiodane - iodosylbenzene - iodosylbenzene diacetate - nitrene
- aziridination - C-H insertion - copper catalyst - rhodiumcatalyst - total synthesis
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