New and Facile Entry to Nitrilium Phosphane Ylide Complex Chemistry by Using 7-Phosphanorbornadiene Complexes

Abstract

Highly reactive nitrilium phosphane ylide complexes 1 are formed as intermediates in the thermal decomposition of 7‐phosphanorbornadiene complexes in the presence of 1‐piperidinonitrile. They react with dimethylacetylenedicarboxylate in [3+2] cycloadditions to give 2H‐1,2‐azaphosphole complexes. pip=1‐piperidino; R=Me, Ph.

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

“…Unstable transient adducts have been also postulated on the basis of trapping reactions. This is the case with piperidine-1-carbonitrile [49] (Eqn. 6).…”

A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non‐covalent Interactions

“…In contrast, N,P,C cage formation involving transient cycloaddition reactions of 1,3‐dipoles such as nitrilium phosphane ylide complexes16 is rare,17 because the only established route to these transient 1,3‐dipole species relies on reactions of thermally formed electrophilic terminal phosphinidene complexes18 with nitriles at elevated temperatures 19. 20 However, some evidence for a transient 1,3‐dipole was obtained recently, through the formation of P ‐iminoyl phosphane complexes in the reaction of a Li/Cl phosphinidenoid complex and dimethylcyanamide;21 the formation of a C ‐amino‐substituted 2 H ‐azaphosphirene complex pointed in the same direction.…”

Intramolecular [3+2] Cycloaddition of a Nitrilium Phosphane Ylide Complex to theP-Phenyl Group of a Wittig Ylide

“…Nitrilium phosphane ylide complexes VI , whose existence as intermediates we were able to demonstrate by trapping reactions,6 now represent a new and well‐established 1,3‐dipole system in heterocyclic chemistry 7–9. We recently discovered the 1,1‐addition of electrophilic terminal phosphanediyl complexes IV to nitriles V , providing an independent access to VI (Scheme ), so that the synthetic potential of VI could be extended further by the use of 7‐phosphanorbornadiene complexes 10, 11…”