Non-conventional Behavior of a 2,1-Benzazaphosphole: Heterodiene or Hidden Phosphinidene?

ABSTRACT: The titled 2,1-benzazaphosphole (1) (i. e. ArP, where Ar=2-(DippN=CH)C₆ H₄ , Dipp=2,6-iPr₂ C₆ H₃ ) showed a spectacular reactivity behaving both as a reactive heterodiene in hetero-Diels-Alder (DA) reactions or as a hidden phosphinidene in the coordination toward selected transition metals (TMs). Thus, 1 reacts with electron-deficient alkynes RC≡CR (R=CO₂ Me, C₅ F₄ N) giving 1-phospha-1,4-dihydro-iminonaphthalenes 2 and 3, that undergo hydrogen migration producing 1-phosphanaphthalenes 4 and 5. Compound 1 is also able to activate the C=C double bond in selected N-alkyl/aryl-maleimides RN(C(O)CH)₂ (R=Me, tBu, Ph) resulting in the addition products 7-9 with bridged bicyclic [2.2.1] structures.

SUBMITTER: Kremlacek V 

PROVIDER: S-EPMC8518707 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature