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Transformation Routes of P V ‐ and P III ‐ N ‐Substituted Acyclic Diaminocarbenes
Author(s) -
Marchenko Anatoliy,
Koidan Georgyi,
Hurieva Anastasiya,
Vlasenko Yurii,
Rozhenko Alexander B.,
Sotiropoulos JeanMarc,
Kostyuk Aleksandr
Publication year - 2019
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201801141
Subject(s) - chemistry , morpholine , isomerization , deprotonation , medicinal chemistry , yield (engineering) , substituent , electrophile , isopropyl , amine gas treating , electrophilic aromatic substitution , stereochemistry , organic chemistry , ion , catalysis , materials science , metallurgy
Herein we report on the synthesis of a set of transient N ‐(P III )‐phosphanyl and N ‐(P V )‐phosphoroselenoyl acyclic diaminocarbenes by deprotonation of the corresponding formamidinium salts. It is shown that N ‐(P V )‐substituted acyclic diaminocarbenes undergo 1,2‐phosphorus shift. Transformations of N ‐(P III )‐substituted acyclic diaminocarbenes result in tetrahydroquinazolines as final products. The proposed mechanism includes the isomerization of the carbenes into transient azomethine ylides followed by their cyclization via electrophilic aromatic substitution. Introduction of the electron‐donating dimetylamino group into the phenyl substituent markedly enhances the rate of the reaction and the yield of the final product. In the case of the morpholine derivative, the corresponding azomethine ylide undergoes opening the morpholine ring giving vinyloxazolidin‐2‐amine. The results are corroborated by DFT calculations.