Premium
Synthesis of Extended Polyphosphacumulenes
Author(s) -
Martin David,
Tham Fook S.,
Baceiredo Antoine,
Bertrand Guy
Publication year - 2006
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200600829
Subject(s) - methylene , phosphorane , deprotonation , chemistry , yield (engineering) , medicinal chemistry , cumulene , alkylation , lithium (medication) , nucleophile , trifluoromethanesulfonate , stereochemistry , pincer movement , derivative (finance) , molecule , organic chemistry , catalysis , physics , ion , medicine , financial economics , economics , thermodynamics , endocrinology
Addition of two equivalents of (Me 3 Si) 2 CLiCl to the C ‐[(diphenyl) (diisopropylamino)phosphonio]‐ P ‐(diisopropylamino)phosphaalkene 2 affords the 1σ 4 ,3σ 3 ‐diphosphabuta‐1,2,3‐triene E1 in 55 % yield. Derivative E1 was fully characterized, including a single‐crystal X‐ray diffraction study. Alkylation of E1 with methyl trifluoromethanesulfonate gives rise to the first C ‐phosphonio‐bis(methylene)phosphorane 5 , which was isolated in 84 % yield. Because the second carbon center is also nucleophilic, cumulene E1 reacts as a “pincer” with BF 3 ⋅OEt 2 , leading to the formation of a novel four‐membered PCBC heterocycle 6 with a betaine‐like structure. Addition of three equivalents of P ‐[diphenyl(diisopropylamino)]methylene phosphorane to (diisopropylamino)dichlorophosphane, followed by addition of one equivalent of CCl 4 , and subsequent deprotonation with lithium hexamethyldisilazide gave rise to 1σ 4 ,3σ 3 ,5σ 4 ‐triphosphapenta‐1,2,3,4‐tetraene F1 , which was isolated in 62 % yield.