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A Convenient Approach to N ‐(Di‐ tert ‐butylphosphanyl)‐ and N ‐(Di‐ tert ‐butylphosphoroselenoyl)formamidinium Salts: Carbene Precursors
Author(s) -
Marchenko Anatoliy,
Koidan Georgyi,
Hurieva Anastasiya,
Savateev Aleksandr,
Rozhenko Alexander B.,
Sotiropoulos JeanMarc,
Shishkina Svitlana V.,
Shishkin Oleg V.,
Kostyuk Aleksandr
Publication year - 2014
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.201301365
Subject(s) - chemistry , dimer , carbene , medicinal chemistry , deprotonation , electrophile , alkyl , formamidinium , organic chemistry , iodide , ion , catalysis
The reactions of (di‐ tert ‐butylphosphanyl)amines and P , P ‐di‐ tert ‐butylphosphinoselenoic amides with Alder's dimer were studied. For di‐ tert ‐butylphosphanylamines, the reaction proceeds by primary electrophilic attack of Alder's dimer at the phosphorus atom to afford a dicationic salt 3 . The deprotonation of 3 led to N ‐phosphanylformamidine 5 (“phosfam”). Alkyl(di‐ tert ‐butylphosphanyl)amines reacted with Alder's dimer in a 2:1 molar ratio to give N ‐phosphanylformamidinium salts; the second equivalent of (alkylamino)phosphane acts as a base. (Arylamino)phosphanes reacted with Alder's dimer to give benzazaphospholium derivatives. To direct the electrophilic attack of Alder's dimer at the nitrogen atom, phosphinoselenoic amides were used. They reacted with Alder's dimer at the selenium atom followed by a selenium–phosphorus shift to give N ‐(di‐ tert ‐butylphosphoroselenoyl)formamidinium salts. The phosphinoselenoic amides with bulky substituents (adamantyl, t Bu) underwent cleavage of the N–alkyl bond to afford phosfams. Various key intermediates such as 3 and 22b were isolated and characterized. A convenient method for the synthesis of carbene precursor P III and P V N ‐substituted formamidinium salts was developed.