Dearomatized BIAN alkaline-earth alkyl catalysts for the intramolecular hydroamination of hindered aminoalkenes

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Abstract

Reaction of a sterically encumbered bis(imino)acenapthene (dipp-BIAN) with either potassium alkyl or the heavier alkaline-earth dialkyl [Ae{CH(SiMe3)2}2(THF)2] (Ae = Mg, Ca, Sr) reagents results in dearomatization of the aromatic ligand. The heteroleptic alkaline-earth alkyl species show enhanced stability toward Schlenk-type redistribution but undergo solution exchange when the bis(trimethylsilyl)methyl substituent is replaced by an anionic ligand of lower overall steric demands. In contrast, analogous reactions performed with [Ba{CH(SiMe3)2} 2(THF)] evidenced facile solution redistribution and resulted in an unusual C-C coupling reaction which is suggested to result from a sterically induced reductive process. An assessment of the Mg, Ca, and Sr alkyl compounds as precatalysts for the intramolecular hydroamination of aminoalkenes evidenced enhanced reactivity, which is ascribed to the greater solution stability of the catalytically active species. Most notably the calcium species may even be applied to the high-yielding cyclization of substrates bearing alkyl substitution at either of the alkenyl positions.

LanguageEnglish
Pages206-216
Number of pages11
JournalOrganometallics
Volume33
Issue number1
Early online date11 Dec 2013
DOIs
StatusPublished - 13 Jan 2014

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Earth (planet)
catalysts
Catalysts
Bearings (structural)
alkyl compounds
methylidyne
Ligands
ligands
Cyclization
reagents
calcium
potassium
Ion exchange
Potassium
Substitution reactions
reactivity
substitutes
Calcium
Substrates

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Dearomatized BIAN alkaline-earth alkyl catalysts for the intramolecular hydroamination of hindered aminoalkenes. / Arrowsmith, Merle; Hill, Michael S.; Kociok-Kohn, Gabriele.

In: Organometallics, Vol. 33, No. 1, 13.01.2014, p. 206-216.

Research output: Contribution to journalArticle

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abstract = "Reaction of a sterically encumbered bis(imino)acenapthene (dipp-BIAN) with either potassium alkyl or the heavier alkaline-earth dialkyl [Ae{CH(SiMe3)2}2(THF)2] (Ae = Mg, Ca, Sr) reagents results in dearomatization of the aromatic ligand. The heteroleptic alkaline-earth alkyl species show enhanced stability toward Schlenk-type redistribution but undergo solution exchange when the bis(trimethylsilyl)methyl substituent is replaced by an anionic ligand of lower overall steric demands. In contrast, analogous reactions performed with [Ba{CH(SiMe3)2} 2(THF)] evidenced facile solution redistribution and resulted in an unusual C-C coupling reaction which is suggested to result from a sterically induced reductive process. An assessment of the Mg, Ca, and Sr alkyl compounds as precatalysts for the intramolecular hydroamination of aminoalkenes evidenced enhanced reactivity, which is ascribed to the greater solution stability of the catalytically active species. Most notably the calcium species may even be applied to the high-yielding cyclization of substrates bearing alkyl substitution at either of the alkenyl positions.",
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N2 - Reaction of a sterically encumbered bis(imino)acenapthene (dipp-BIAN) with either potassium alkyl or the heavier alkaline-earth dialkyl [Ae{CH(SiMe3)2}2(THF)2] (Ae = Mg, Ca, Sr) reagents results in dearomatization of the aromatic ligand. The heteroleptic alkaline-earth alkyl species show enhanced stability toward Schlenk-type redistribution but undergo solution exchange when the bis(trimethylsilyl)methyl substituent is replaced by an anionic ligand of lower overall steric demands. In contrast, analogous reactions performed with [Ba{CH(SiMe3)2} 2(THF)] evidenced facile solution redistribution and resulted in an unusual C-C coupling reaction which is suggested to result from a sterically induced reductive process. An assessment of the Mg, Ca, and Sr alkyl compounds as precatalysts for the intramolecular hydroamination of aminoalkenes evidenced enhanced reactivity, which is ascribed to the greater solution stability of the catalytically active species. Most notably the calcium species may even be applied to the high-yielding cyclization of substrates bearing alkyl substitution at either of the alkenyl positions.

AB - Reaction of a sterically encumbered bis(imino)acenapthene (dipp-BIAN) with either potassium alkyl or the heavier alkaline-earth dialkyl [Ae{CH(SiMe3)2}2(THF)2] (Ae = Mg, Ca, Sr) reagents results in dearomatization of the aromatic ligand. The heteroleptic alkaline-earth alkyl species show enhanced stability toward Schlenk-type redistribution but undergo solution exchange when the bis(trimethylsilyl)methyl substituent is replaced by an anionic ligand of lower overall steric demands. In contrast, analogous reactions performed with [Ba{CH(SiMe3)2} 2(THF)] evidenced facile solution redistribution and resulted in an unusual C-C coupling reaction which is suggested to result from a sterically induced reductive process. An assessment of the Mg, Ca, and Sr alkyl compounds as precatalysts for the intramolecular hydroamination of aminoalkenes evidenced enhanced reactivity, which is ascribed to the greater solution stability of the catalytically active species. Most notably the calcium species may even be applied to the high-yielding cyclization of substrates bearing alkyl substitution at either of the alkenyl positions.

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