Remote functionalisation via sodium alkylamidozincate intermediates: access to unusual fluorenone and pyridyl ketone reactivity patterns

James J. Crawford, Ben J. Fleming, Alan R. Kennedy, Jan Klett, Charles T. O'Hara, Samantha A. Orr

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Treating fluorenone or 2-benzoylpyridine with the sodium zincate [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] in hexane solution, gives efficient Bu-t addition across the respective organic substrate in a highly unusual 1,6-fashion, producing isolable organometallic intermediates which can be quenched and aerobically oxidised to give 3-tert-butyl-9H-fluoren-9-one and 2-benzoyl-5-tert-butylpyridine respectively.

LanguageEnglish
Pages3772-3774
Number of pages3
JournalChemical Communications (London)
Volume47
Issue number13
DOIs
Publication statusPublished - 11 Jan 2011

Fingerprint

Hexanes
Organometallics
Ketones
Sodium
Substrates
phenyllithium
Na(mu-(t)Bu)(mu-TMP)Zn((t)Bu)
2-benzoyl-9H-fluoren-9-one

Keywords

  • metal-mediated zincation
  • ferroelectric liquid-crystals
  • directed ortho-metalation
  • tertiary aromatic amide
  • structural insights
  • polar order
  • 1,4-dihydropyridines
  • magnesiation
  • derivatives
  • complexes

Cite this

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abstract = "Treating fluorenone or 2-benzoylpyridine with the sodium zincate [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] in hexane solution, gives efficient Bu-t addition across the respective organic substrate in a highly unusual 1,6-fashion, producing isolable organometallic intermediates which can be quenched and aerobically oxidised to give 3-tert-butyl-9H-fluoren-9-one and 2-benzoyl-5-tert-butylpyridine respectively.",
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Remote functionalisation via sodium alkylamidozincate intermediates : access to unusual fluorenone and pyridyl ketone reactivity patterns. / Crawford, James J.; Fleming, Ben J.; Kennedy, Alan R.; Klett, Jan; O'Hara, Charles T.; Orr, Samantha A.

In: Chemical Communications (London), Vol. 47, No. 13, 11.01.2011, p. 3772-3774.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Remote functionalisation via sodium alkylamidozincate intermediates

T2 - Chemical Communications (London)

AU - Crawford, James J.

AU - Fleming, Ben J.

AU - Kennedy, Alan R.

AU - Klett, Jan

AU - O'Hara, Charles T.

AU - Orr, Samantha A.

PY - 2011/1/11

Y1 - 2011/1/11

N2 - Treating fluorenone or 2-benzoylpyridine with the sodium zincate [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] in hexane solution, gives efficient Bu-t addition across the respective organic substrate in a highly unusual 1,6-fashion, producing isolable organometallic intermediates which can be quenched and aerobically oxidised to give 3-tert-butyl-9H-fluoren-9-one and 2-benzoyl-5-tert-butylpyridine respectively.

AB - Treating fluorenone or 2-benzoylpyridine with the sodium zincate [(TMEDA)center dot Na(mu-Bu-t)(mu-TMP)Zn(Bu-t)] in hexane solution, gives efficient Bu-t addition across the respective organic substrate in a highly unusual 1,6-fashion, producing isolable organometallic intermediates which can be quenched and aerobically oxidised to give 3-tert-butyl-9H-fluoren-9-one and 2-benzoyl-5-tert-butylpyridine respectively.

KW - metal-mediated zincation

KW - ferroelectric liquid-crystals

KW - directed ortho-metalation

KW - tertiary aromatic amide

KW - structural insights

KW - polar order

KW - 1,4-dihydropyridines

KW - magnesiation

KW - derivatives

KW - complexes

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DO - 10.1039/c1cc10193e

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EP - 3774

JO - Chemical Communications (London)

JF - Chemical Communications (London)

SN - 0009-241X

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