ManganeseIIIBased Peroxidation of Alkenes to Heterocycles

Hiroshi Nishino

Department of Chemistry, Faculty of Science, Kumamoto University, Kurokami 2-39-1,

860-8555 Kumamoto, Japan

[email protected]

1 Naturally Occurring 1,2-Dioxane Derivatives 40

2 History of the Discovery of the 1,2-Dioxane Synthesis

Using Manganese(III) Complexes 40

3 Formation of 1,2-Dioxanes

Using Tris(2,4-pentanedionato)manganese(III) 45

4 Combination of Manganese(III) Acetate with 1,3-Dicarbonyl Compounds . 47

4.1 Reaction Using 1,3-Diketones 47

4.2 Reaction Using ß-Ketoesters 48

4.3 Reaction Using Acetoacetamides 51

4.4 Reaction Using Sulfinyl-, Sulfonyl-, and Phosphinoyl-2-propanones 52

4.5 Reaction Using Acylacetonitrile Building Blocks 53

4.6 Reaction Using Cyclic Amides: 2,3-Pyrrolidinediones, 2,4-Pyrrolidinediones, 4-Piperidine-3-carboxylates, and 2,4-Piperidinediones 55

5 Hydroperoxidation Using Manganese(III) Acetate 59

5.1 Reaction Using Barbituric Acids 59

5.2 Reaction Using Pyrazolidine-3,5-diones 60

5.3 Reaction Using 4-Hydroxy-1H-quinolin-2-ones 62

5.4 Manganese(III)-Catalyzed Direct Hydroperoxidation of Heterocyclic 1,3-Dicarbonyl Compounds 63

6 Spectroscopic Feature and Stereochemistry of 1,2-Dioxan-3-ols 65

7 Mechanism for the Formation of 1,2-Dioxan-3-ols 68

8 Chemical Transformation of the Synthesized 1,2-Dioxane Derivatives ... 70

9 Summary 71

References 72

Abstract Synthesis of endoperoxides and hydroperoxides using tris(2,4-pentanedionato) manganese(III) or manganese(III) acetate is described. The reaction of various alkenes with tris(2,4-pentanedionato)manganese(III) at ambient temperature in air gives 4-acetyl-1,2-dioxan-3-ols. The manganese(III) acetate-catalyzed aerobic oxidation of various al-

kenes in the presence of various 1,3-dicarbonyl compounds also gives the corresponding 1,2-dioxan-3-ols. The basic skeleton of naturally occurring heterocycle-fused endoperoxides can be produced by the manganese(III)-catalyzed aerobic oxidation. On the other hand, a similar reaction using barbituric acids, pyrazolidinediones, and hydroxyquinoli-nones gives bis(hydroperoxyethyl) derivatives. In addition, the direct hydroperoxidation of the cyclic amides occurs in the absence of alkenes. The spectroscopic features, stereochemistry, mechanism for the formation of 1,2-dioxan-3-ols, and synthetic application are also mentioned.

Keywords 1,2-Dioxan-3-ols • Aerobic oxidation • Endoperoxidation • Hydroperoxidation • Manganese(III) acetate

0 0

Post a comment