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

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

doi:10.1021/acs.organomet.5b00979

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

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

School of Chemistry

Research output: Contribution to journal › Article › Other › peer-review

9 Citations (Scopus)

Abstract

An unexpected aza-enolate propyl addition complex, [(PhC=CH₂)(CH=C(CH₂CH₂CH₃)CH₃)NNa·THF]_∞ (1), was isolated when (S)-N-α-(methylbenzyl)allylamine reacted in hexane with nBuNa in the presence of THF. Analytical studies revealed a decomposition of the sodium 1-azaallylamide to a sodium enamide and propene, identified by solution studies and a GC-headspace study, respectively. Propene then adds to the carbanion tautomer of the sodium 1-azaallylamide followed by anionic rearrangements to later form the aza-enolate propyl addition complex.

Original language	English
Pages (from-to)	303-305
Number of pages	3
Journal	Organometallics
Volume	35
Issue number	3
DOIs	https://doi.org/10.1021/acs.organomet.5b00979
Publication status	Published - 8 Feb 2016

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10.1021/acs.organomet.5b00979

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abstract = "An unexpected aza-enolate propyl addition complex, [(PhC=CH2)(CH=C(CH2CH2CH3)CH3)NNa·THF]∞ (1), was isolated when (S)-N-α-(methylbenzyl)allylamine reacted in hexane with nBuNa in the presence of THF. Analytical studies revealed a decomposition of the sodium 1-azaallylamide to a sodium enamide and propene, identified by solution studies and a GC-headspace study, respectively. Propene then adds to the carbanion tautomer of the sodium 1-azaallylamide followed by anionic rearrangements to later form the aza-enolate propyl addition complex.",

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AU - Koutsaplis, Magdaline

AU - Andrews, Philip C.

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N2 - An unexpected aza-enolate propyl addition complex, [(PhC=CH2)(CH=C(CH2CH2CH3)CH3)NNa·THF]∞ (1), was isolated when (S)-N-α-(methylbenzyl)allylamine reacted in hexane with nBuNa in the presence of THF. Analytical studies revealed a decomposition of the sodium 1-azaallylamide to a sodium enamide and propene, identified by solution studies and a GC-headspace study, respectively. Propene then adds to the carbanion tautomer of the sodium 1-azaallylamide followed by anionic rearrangements to later form the aza-enolate propyl addition complex.

AB - An unexpected aza-enolate propyl addition complex, [(PhC=CH2)(CH=C(CH2CH2CH3)CH3)NNa·THF]∞ (1), was isolated when (S)-N-α-(methylbenzyl)allylamine reacted in hexane with nBuNa in the presence of THF. Analytical studies revealed a decomposition of the sodium 1-azaallylamide to a sodium enamide and propene, identified by solution studies and a GC-headspace study, respectively. Propene then adds to the carbanion tautomer of the sodium 1-azaallylamide followed by anionic rearrangements to later form the aza-enolate propyl addition complex.

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

Abstract

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Early Main Group Organometallic Complexes and their Role in Asymmetric Synthesis

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

Abstract

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Early Main Group Organometallic Complexes and their Role in Asymmetric Synthesis

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