Aminonitrenes. addition

A -Amino- and A-substituted amino-pyrroles readily undergo Diels-Alder additions and add to activated alkynes at room temperature. The resulting azanorbornadienes extrude A-aminonitrenes and this forms the basis of an unusual synthesis of benzene derivatives (81S753,81TL3347). It has been found that ethyl/3-phenylsulfonylpropiolate (135) is a superior dienophile to DMAD (Scheme 50). 

N- Aminopyrroles undergo Diels-Alder addition with alkynes bearing electron-withdrawing groups. Loss of N- aminonitrene from the resulting adducts yields benzenoid derivatives (Scheme 68) (81TL1767) (see also Section 3.02.2.10). 

A remarkable intramolecular addition of aminonitrenes to a double bond across space leads to the cage compounds 362.414... 

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