Benzyne Addition to Dialkylanilines<sup>1a,b</sup>

Lepley, Arthur R.; Giumanini, Angelo G.; Giumanini, Armida B.; Khan, Wajid

doi:10.1021/jo01345a002

Cited by 23 publications

(21 citation statements)

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“…[93,94] Vor der Metallierung liegt in Hexan eine synergetische Lithiumzinkatmischung aus LTMP und tBu 2 Zn vor, die mit dem Amid zum 1:1-Donor-Akzeptor-Komplex [{(iPr) 2 NC(Ph)( = O)}Li(m-tmp) (m-tBu)Zn(tBu)] (88) Was speziell die gerichtete Metallierung betrifft, wurden die interessantesten Ergebnisse bei AMMZ-Reaktionen von Anilinderivaten beobachtet. [96] Das mit einem schwach ortho-dirigierenden Substituenten ausgestattete N,N-Dimethylanilin geht mit PhLi [97] und BuLi [98] ortho-Metallierungen ein, wobei im ersten Fall geringe Ausbeuten und im zweiten Fall hohe Ausbeuten resultieren. Im markanten Unterschied dazu lenkt das Natrium-TMP-Zinkat 83 die Deprotonierung in die meta-Position, und der kristalline Komplex [(tmeda)Na(m-Ar*)(m-tmp)Zn(tBu)] (95; Ar* = 3-C 6 H 4 NMe 2 ) wird isoliert.…”

Section: Aufsätzeunclassified

Deprotonierende Metallierungen mit 'at‐Verbindungen: Synergie, Synthese und Strukturaufbau

Mongin²,

et al. 2007

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In der organischen Synthesechemie werden Monometallspezies wie Organolithiumverbindungen seit langem für Deprotonierungsreaktionen genutzt. In den letzten Jahren ist mit den 'at‐Komplexen eine neue Klasse von Metallierungsreagentien hinzugetreten, die das Syntheserepertoire metallorganischer Spezies ergänzt. Dank eines frei wählbaren Metallzentrums (Magnesium, Zink oder Aluminium), frei wählbarer Liganden (in Art und Anzahl) und eines frei wählbaren sekundären Metallzentrums (eines Alkalimetalls wie Lithium oder Natrium) sind 'at‐Komplexe äußerst vielseitige basische Reagentien, deren synergetische Reaktionsweisen mit den homometallischen Magnesium‐, Zink‐ oder Aluminiumverbindungen nicht beobachtet werden. Deprotonierungen mit metallorganischen 'at‐Komplexen haben neue Perspektiven in der organischen Chemie eröffnet, mit ungewöhnlichen Reaktivitäten und manchmal unvorhergesehenen Regioselektivitäten.

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Section: Aufsätzeunclassified

Deprotonierende Metallierungen mit 'at‐Verbindungen: Synergie, Synthese und Strukturaufbau

Mongin²,

et al. 2007

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“…Note only metals shown for clarity. Reagents and conditions: [a] n BuLi, hexane, reflux, 16 h; [b] n BuNa, hexane, 0 °C; [c] [NaTMP( t Bu)Zn( t Bu)], hexane, reflux, 2 h, [d] [Na 4 Mg 2 (TMP) 6 ( n Bu) 2 ], methylcyclohexane, reflux, 4 h, [e] n BuLi.TMEDA, hexane…”

Section: Introductionmentioning

confidence: 99%

Contrasting Synergistic Heterobimetallic (Na–Mg) and Homometallic (Na or Mg) Bases in Metallation Reactions of Dialkylphenylphosphines and Dialkylanilines: Lateral versus Ring Selectivities

Stevens

Hashim

Gwee

et al. 2018

Chemistry A European J

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A series of dialkylphenylphosphines and their analogous aniline substrates have been metallated with the synergistic mixed-metal base [(TMEDA)Na(TMP)(CH SiMe )Mg(TMP)] 1. Different metallation regioselectivities for the substrates were observed, with predominately lateral or meta-magnesiated products isolated from solution. Three novel heterobimetallic complexes [(TMEDA)Na(TMP)(CH PCH Ph)Mg(TMP)] 2, [(TMEDA)Na(TMP)(m-C H PiPr )Mg(TMP)] 3 and [(TMEDA)Na(TMP)(m-C H NEt )Mg(TMP)] 4 and two homometallic complexes [{(TMEDA)Na(EtNC H )} ] 5 and [(TMEDA)Na (TMP)(C H PEt)] 6 derived from homometallic metallation have been crystallographically characterised. Complex 6 is an unprecedented sodium-amide, sodium-phosphide hybrid with a rare (NaNNaP) ladder motif. These products reveal contrasting heterobimetallic deprotonation with homometallic induced ethene elimination reactivity. Solution studies of metallation mixtures and electrophilic iodine quenching reactions confirmed the metallation sites. In an attempt to rationalise the regioselectivity of the magnesiation reactions the C-H acidities of the six substrates were determined in THF solution using DFT calculations employing the M06-2X functional and cc-pVTZ Dunning's basis set.

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“…Thus as seen in Tables I and 11, as the base-salt ratio increases the 4/5 value decreases (14) J. E. Baldwin and J. E. Brown, J . Thus as seen in Tables I and 11, as the base-salt ratio increases the 4/5 value decreases (14) J. E. Baldwin and J. E. Brown, J .…”

mentioning

confidence: 76%

“…The white crystalline product (58 g, 84% yield) was collected at 195-197" (24 mm) [lit,.40 198-199' (18 mm) Anal. Found: C,72.41;H ,7.45;N ,5.40;C1,14.06. Found: C,72.41;H ,7.45;N ,5.40;C1,14.06.…”

Section: N-methylmentioning

confidence: 99%

Quaternary benzylammonium ion rearrangements with organolithium compounds. V. Reaction of N,N-dimethyl-N-benzylanilinium halides

Lepley¹,

Giumanini²

1971

J. Org. Chem.

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A new rearrangement product, N-methyl-N-(wphenethy1)aniline (4), and a new cleavage product, N-methyl-AJ-benzylaniline (j), have been observed in reactions of N,N-dimethyl-N-beneylanilinium ion (1) with organolithium bases. N-Methyl-lV-(p-phenyl)aniline ( 5 ) was directly isolated from reaction mixtures, whereas it is destroyed by sodium amide. The Sommelet rearrangement product, N-methyl-it7-(0-xyly1)aniline ( 6 ) , was observed in very small quantities because of the benzylation of its 0-Li precursor by the starting salt, to give a dimeric product. Cleavage reactions of the quaternary benzylanilinium salt with potassium hydroxide and sodium ethoxide in refluxing ethanol also gave 3 in addition to the principal products, X,N-dimethylaniline (2) and ethyl benzyl ether. Analogous cleavage products were observed with organolithium reagents plus significant amounts of trans-stilbene (8). The effects of concentration, ether-hexane solvent mixtures, and anion of the salt on the ratios of rearrangement and cleavage products were studied for n-butyllithium reactions and are interpreted in terms of dianion and radical pair mechanisms.

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Benzyne Addition to Dialkylanilines^1a,b

Cited by 23 publications

References 1 publication

Deprotonierende Metallierungen mit 'at‐Verbindungen: Synergie, Synthese und Strukturaufbau

Deprotonierende Metallierungen mit 'at‐Verbindungen: Synergie, Synthese und Strukturaufbau

Contrasting Synergistic Heterobimetallic (Na–Mg) and Homometallic (Na or Mg) Bases in Metallation Reactions of Dialkylphenylphosphines and Dialkylanilines: Lateral versus Ring Selectivities

Quaternary benzylammonium ion rearrangements with organolithium compounds. V. Reaction of N,N-dimethyl-N-benzylanilinium halides

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Benzyne Addition to Dialkylanilines1a,b

Cited by 23 publications

References 1 publication

Deprotonierende Metallierungen mit 'at‐Verbindungen: Synergie, Synthese und Strukturaufbau

Deprotonierende Metallierungen mit 'at‐Verbindungen: Synergie, Synthese und Strukturaufbau

Contrasting Synergistic Heterobimetallic (Na–Mg) and Homometallic (Na or Mg) Bases in Metallation Reactions of Dialkylphenylphosphines and Dialkylanilines: Lateral versus Ring Selectivities

Quaternary benzylammonium ion rearrangements with organolithium compounds. V. Reaction of N,N-dimethyl-N-benzylanilinium halides

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Benzyne Addition to Dialkylanilines^1a,b