The Strange Case of Sodium (<i>S</i>)-<i>N</i>-α-(Methylbenzyl)allylamide: Anion Rearrangement, Decomposition, and a Peculiar Propyl Addition

Border, Emily Chantelle; Koutsaplis, Magdaline; Andrews, Philip C.

doi:10.1021/acs.organomet.5b00979

Cited by 9 publications

(9 citation statements)

References 21 publications

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“…There is, as yet, no other evidence of this polymerization process occurring, although surprisingly styrene has never been isolated as a byproduct, despite many attempts, suggesting that it must be consumed in situ. We recently reported a similar decomposition process with ( S )- N -α-(methylbenzyl)allyl amine where decomposition of the sodium 1- aza -allyl amide species results in the formation of the same enamide as observed here and propene . Propene was found to be extremely reactive toward the anionic species in solution, resulting in addition.…”

Section: Results and Discussionsupporting

confidence: 70%

“…We recently reported a similar decomposition process with (S)-N-α-(methylbenzyl)allyl amine where decomposition of the sodium 1-aza-allyl amide species results in the formation of the same enamide as observed here and propene. 11 Propene was found to be extremely reactive toward the anionic species in solution, resulting in addition.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Metal-Induced C–N Bond Cleavage in the Decomposition of Alkali (R,R)-Bis(α-methylbenzyl)amide Complexes

et al. 2017

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This study resulted in the isolation of new alkali metal complexes of (R,R)-bis(α-methylbenzyl)amine (B-α-mba) characterized by NMR spectroscopy and singlecrystal X-ray diffraction where possible. The reaction outcome was found to be dependent on metal and Lewis donor choice to afford species [{PhCH and [{PhCH(CH 3 )} 2 NNa•(THF) k ] n 5 as simple amido species. Complex [{PhC(CH 2 )}{PhCH(CH 3 )}NNa•TMEDA] ∞ 6 was isolated as a result of a β-hydride elimination. A complex mixture of species was isolated when B-α-mba was reacted with potassium in the presence of TMEDA and PMDETA to give speciesIn both cases, the decomposition to form the potassium enamide species 7c and 8c was the more favorable process. The decomposition reaction of B-α-mba with nBuNa in the presence of PMDETA to give the sodium enamide [PhC(CH 2 )N(H)Na•PMDETA] 1 was investigated with GC-MS studies revealing the byproduct of this decomposition as styrene.

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Section: Results and Discussionsupporting

confidence: 70%

Section: ■ Results and Discussionmentioning

confidence: 99%

Metal-Induced C–N Bond Cleavage in the Decomposition of Alkali (R,R)-Bis(α-methylbenzyl)amide Complexes

et al. 2017

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“…In recent years, we have studied alkali metal allylic amide systems − owing to the simple building block having a significant role in accessing many valuable N-containing compounds such as β-amino acids and β-lactams, , chiral β-branched esters, chiral 1,2 diamines, and peptide isosteres . Our ongoing interest in allylic amide systems and their applications has led us to delve into the phosphorus derivatives exploiting both oxidation states, where P(V) is air-stable over the P(III) analogues.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Solution Studies of Lithiated Allylic Phosphines and Phosphine Oxides

et al. 2020

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This study reports a new series of 12 α-lithiated allylic phosphines and phosphine oxides. By incorporating Lewis base donors including diethyl ether (Et 2 O), tetrahydrofuran (THF), N,N,N′,N′,tetramethylethylenediamine (TMEDA), and N,N,N′,N′,N″,-pentamethyldiethylenetriamine (PMDETA), nine complexes were structurally characterized by single-crystal X-ray crystallography. This includes novel dilithiated allylic phosphine 4 [PhP{CHCHCH 2 Li(TMEDA)} 2 ] and a rare hemisolvated lithiated phosphine oxide 6 [{Ph 2 P(O)CHC(Me)-CH 2 Li} 2 (TMEDA)]. Interestingly, in the solid state, P(III) complexes take advantage of Li−π interactions to the newly formed delocalized system, in comparison to P(V) complexes where the oxophillic nature of the lithium atom dominates. All 12 complexes were fully characterized in the solution state by multinuclear NMR spectroscopy. DFT calculations on isomers of monomeric lithiated complex 3 [Ph 2 PCHC(Me)CH 2 Li(PMDETA)] described the low energy barrier between transition steps of the subtle delocalization of the allylic chain. Article pubs.acs.org/Organometallics

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“…4 Our own research has shown alkali-metal sources 16,29 also to be effective. However, in this study 5 and 6…”

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confidence: 99%

The importance of the Lewis base in lithium mediated metallation and bond cleavage reaction of allyl amines and allyl phosphines

2016

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Metallation of two analogous N- and P-allyl molecules Ph2NCH2CHCH2 and Ph2PCH2CHCH2 with nBuLi have shown contrasting reactivities based on the choice of Lewis donor. With metallation of the alpha carbon atom was achieved regardless of the Lewis donor used while in comparison metallation of showed an unexpected donor denticity dependence with P-C bond clevage induced with the tri-dentate PMDETA. Complementary DFT and solution studies rationalise this outcome.

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The Strange Case of Sodium (S)-N-α-(Methylbenzyl)allylamide: Anion Rearrangement, Decomposition, and a Peculiar Propyl Addition

Cited by 9 publications

References 21 publications

Metal-Induced C–N Bond Cleavage in the Decomposition of Alkali (R,R)-Bis(α-methylbenzyl)amide Complexes

Metal-Induced C–N Bond Cleavage in the Decomposition of Alkali (R,R)-Bis(α-methylbenzyl)amide Complexes

Synthesis, Structure, and Solution Studies of Lithiated Allylic Phosphines and Phosphine Oxides

The importance of the Lewis base in lithium mediated metallation and bond cleavage reaction of allyl amines and allyl phosphines

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