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The reduction of the 1‐phospha‐2‐azanorbornene derivate  endo ‐ 1  with lithium aluminium hydride leads to an unprecedented 1‐phosphabicyclo[3.2.1]octa‐2,5‐diene, while a phospholide anion is formed with lithium. The latter can be protonated resulting in formation of an unusual 2 H ‐phosphole dimer. Furthermore, 3 H ‐phospholes, previously assumed to have no synthetic relevance as intermediates, were proposed to act as dienophile in the dimerisation of 3,4‐dimethyl‐1‐phenylphosphole at elevated temperatures based on theoretical calculations.

Reductive Rearrangement of a 1‐Phospha‐2‐azanorbornene