Catalytic Activation of Silylated Nucleophiles Using tBu‐P4 as a Base.

Abstract

Substitution reactions O 0040Catalytic Activation of Silylated Nucleophiles Using tBu-P4 as a Base. -The phosphorus compound is found to be an efficient catalyst for the reaction of silylated O-, N-, and C-nucleophiles with various electrophiles. -(UENO, M.; HORI, C.; SUZAWA, K.; EBISAWA, M.; KONDO*, Y.; Eur.

Phosphazene: Preparation, Reaction and Catalytic Role

“…The reaction of o-iodofluorobenzene was also examined and the iodophenyl aryl ether was obtained in 43% yield (run 7). The reverse and complimentary regioselectivity to transition metal catalysed reactions is attractive for selective functionalization of aromatic compounds [54]. As above described, t Bu-P4 base was found to catalyse the coupling reaction of aryl fluorides with silyl ethers.…”

“…The activation of the nucleophile-silicon bond is important for the generation of a reactive anion to achieve a new bond formation. A novel catalytic activation of various O-, N-, and C-nucleophile-silicon bonds using a t Bu-P4 base has been investigated to perform reactions with various elecrophiles [54] (Figure 5.4).…”

“…The tolerance of the bromo or iodo group is very attractive for the subsequent transformation; the conventional metal catalysed reactions do not allow this kind of selectivity. When tetrabutylammonium fluoride (TBAF) was employed as a catalyst, the reaction was very sluggish and only a trace amount of product was obtained [54] (run 9).…”

Deprotonative Functionalization of the Difluoromethyl Group

“…31,32 Two other silylated electrophiles were assessed with LDA. Me2PhSiCl gave a comparable yield in contrast to t-BuMe2SiCl which afforded 23% of 2c in accordance with literature 33.…”