Anion Rearrangements of Alkali Metal Complexes of the Chiral Amine (S)-N-alpha-(Methylbenzyl)phenylallylamine: Structural and Solution Insights

作者：Andrews Philip C^*; Blair Victoria L; Koutsaplis Magdaline; Thompson Christopher D

来源：Organometallics, 2012, 31(23): 8135-8144.

DOI：10.1021/om300747w

Reaction of the chiral amine (S)-N-alpha-(methylbenzyl)phenylallylamine, [(S)-N-alpha-mbpa], with nBuM (M = Li, Na, K) in the presence of the Lewis donors TMEDA or THF (TMEDA = N,N,N%26apos;,N%26apos;-tetramethylethylenediamine, THF = tetrahydrofuran) resulted in a series of mono- or dimetalated complexes, [{PhC(H)CH3NC-(H)C(H)C(H)PhLi2(TMEDA)(2)] 1, [{PhC(H)CH3NCH=CHCH2PhNa(TMEDA)](2) 2, and [PhC(=CH2)N-(CH2CH2CH3)K](infinity) 3, being formed with various 1,3-sigmatropic rearranged allylic bonding patterns. Completing previous work on the related amine N-alpha-(methylbenzyl)allylamine, the potassiated aza-enolate complex [(R)-{(PhC(=CH2)N(CH2CH2CH3(THF)](infinity), 4 is also reported. All four complexes 1-4 have been characterized by single-crystal X-ray diffraction and solution NMR spectroscopy studies. DTF calculations on model systems investigated the preference for the monomeric Li-2-mbpa 1 to undergo isomerization to the aza-allyl anion conformation, which, interestingly, is more energetically stable as a monomeric complex.

• 出版日期2012-12-10