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

doi:10.1039/c1cc10193e

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

Pure And Applied Chemistry

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

19 Citations (Scopus)

113 Downloads (Pure)

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.

Original language	English
Pages (from-to)	3772-3774
Number of pages	3
Journal	Chemical Communications (London)
Volume	47
Issue number	13
DOIs	https://doi.org/10.1039/c1cc10193e
Publication status	Published - 11 Jan 2011

Keywords

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

Access to Document

10.1039/c1cc10193e

C1cc10193eFinal published version, 1.11 MBLicence: Unspecified

ENANTIOSELECTIVE APPLICATIONS OF DESIGNER SYNERGIC REAGENTS (First Grant)
O'Hara, C. (Principal Investigator)
EPSRC (Engineering and Physical Sciences Research Council)
1/10/08 → 31/03/12
Project: Research
Physical Organic Chemistry: Opportunities In Synthesis, Materials And Pharmaceuticals (Science And Innovation Award)
Murphy, J. (Principal Investigator), Coombs, G. (Co-investigator), Ferguson, A. (Co-investigator) & Florence, A. (Co-investigator)
Scottish Funding Council SFC, EPSRC (Engineering and Physical Sciences Research Council)
1/09/07 → 30/10/12
Project: Research

x-ray diffractometer
Kennedy, A.
Pure And Applied Chemistry
Facility/equipment: Equipment

Cite this

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

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.",

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

author = "Crawford, {James J.} and Fleming, {Ben J.} and Kennedy, {Alan R.} and Jan Klett and O'Hara, {Charles T.} and Orr, {Samantha A.}",

year = "2011",

month = jan,

day = "11",

doi = "10.1039/c1cc10193e",

language = "English",

volume = "47",

pages = "3772--3774",

journal = "Chemical Communications (London)",

issn = "0009-241X",

publisher = "Chemical Society",

number = "13",

}

TY - JOUR

T1 - Remote functionalisation via sodium alkylamidozincate intermediates

T2 - access to unusual fluorenone and pyridyl ketone reactivity patterns

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

U2 - 10.1039/c1cc10193e

DO - 10.1039/c1cc10193e

M3 - Article

SN - 0009-241X

VL - 47

SP - 3772

EP - 3774

JO - Chemical Communications (London)

JF - Chemical Communications (London)

IS - 13

ER -

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

Abstract

Keywords

Access to Document

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Projects

ENANTIOSELECTIVE APPLICATIONS OF DESIGNER SYNERGIC REAGENTS (First Grant)

Physical Organic Chemistry: Opportunities In Synthesis, Materials And Pharmaceuticals (Science And Innovation Award)

Equipment

x-ray diffractometer

Cite this