HETARYLDIENES: PROMISING BUILDING BLOCKS TO NEW POLYHETARYL DERIVATIVES

György Hajós and András Kotschy*

Chemical Center, Institute of Chemistry, Hungarian Academy of Sciences H-1525 Budapest POBox 17
*Present address: Eötvös Loránd University, General and Inorganic Department of Chemistry

I. SYNTHESIS

A. Syntheses involving compilation of the diene chain
A.1.Wittig-type syntheses A.1.1. Starting from hetaryl aldehydes A.1.2. Starting from hetaryl acroleins A.1.3. Starting from hetarylphosphoranes A. 1.4. Starting from hetarylmethylene phosphonic esters A.2. Synthesis of the diene chain by the use of other condensation reactions A.2.1. From methyl substituted hetarenes A.2.2. By miscellaneous condensation reactions A.3. Synthesis of the diene chain by other methods A.3.1. From a nitrile with Grignard reagent A.3.2. Syntheses utilising dehydration A.3.3. Synthesis of the diene chain dehydrobromation A.3.4. Formation of the diene chain by oxo-enol tautomerism A.3.5. Peterson olefin formation

B. Synthesis of hetaryldienes from other functionalised polyenes
B.1. Cross-coupling reaction of substituted dienes B.2. Ring closure reaction to hetarenes starting from substituted dienes B.2.1. Formation of 5-membered rings B.2.2. Formation of 6-membered rings

C. Formation of hetaryldienes by ring opening reactions
C.1. Ring opening of neutral systems C.2. Ring opening of positively charged systems with a bridge head nitrogen atom C.3. Ring opening of partially reduced fused systems with bridge-head nitrogen atom

D. Synthesis of hetaryldienes by rearrangements.

E. Collective Table

II. REACTIONS

F. Structure and reactivity

G. Reactions with electrophiles
G.1. Protonation G.2. Reaction with other electrophiles

H. Cycloaddition reactions
H.1. Dienes as 4p components H.1.1. Diels-Alder (4+2) cycloadditions H.1.2. 4+6 cycloadditions H.2. Dienes as 2p components H.2.1. 2+2 cycloadditions H.2.2. 2+3 cycloadditions H.2.3. "Inverse electron-demand" Diels-Alder (2+4) cycloadditions H.2.4. 2+8 cycloadditions

I. Rearrangements

J. Miscellaneous transformations

III. LITERATURE