Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)(2) and applications in in situ cross coupling reactions

Victoria L. Blair; David C. Blakemore; Duncan Hay; Eva Hevia; David C. Pryde

doi:10.1016/j.tetlet.2011.06.090

Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)(2) and applications in in situ cross coupling reactions

Victoria L. Blair, David C. Blakemore, Duncan Hay, Eva Hevia, David C. Pryde

Pure And Applied Chemistry

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

31 Citations (Scopus)

Abstract

This study investigates the ability of the mixed-metal reagent [Li(TMP)Zn(tBu)(2)] 1 to promote direct Zn-H exchange reactions (zincations) of a wide range of N-heterocyclic molecules. The generated metallated intermediates from these reactions are intercepted with I-2 and some of them are also employed as precursors in Pd-catalysed Negishi cross-coupling applications. A comparison with recent precedents in metallation chemistry reveals that for some of these heterocycles, 1 allows improved conversions, under milder conditions and in certain cases, even gives unique regioselectivities.

Original language	English
Pages (from-to)	4590-4594
Number of pages	5
Journal	Tetrahedron Letters
Volume	52
Issue number	36
DOIs	https://doi.org/10.1016/j.tetlet.2011.06.090
Publication status	Published - 7 Sept 2011

Keywords

metallation
zincation
N-Heterocycles
lithium
mixed-metal reagents
directed ortho-metalation
polysubstituted aromatics
functionalized aromatics
structual basis
magnesium
lithiation
bases
efficient
diazines
pyrazines

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10.1016/j.tetlet.2011.06.090

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title = "Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)(2) and applications in in situ cross coupling reactions",

abstract = "This study investigates the ability of the mixed-metal reagent [Li(TMP)Zn(tBu)(2)] 1 to promote direct Zn-H exchange reactions (zincations) of a wide range of N-heterocyclic molecules. The generated metallated intermediates from these reactions are intercepted with I-2 and some of them are also employed as precursors in Pd-catalysed Negishi cross-coupling applications. A comparison with recent precedents in metallation chemistry reveals that for some of these heterocycles, 1 allows improved conversions, under milder conditions and in certain cases, even gives unique regioselectivities.",

keywords = "metallation, zincation, N-Heterocycles, lithium, mixed-metal reagents, directed ortho-metalation, polysubstituted aromatics, functionalized aromatics, structual basis, magnesium, lithiation, bases, efficient, diazines, pyrazines",

author = "Blair, {Victoria L.} and Blakemore, {David C.} and Duncan Hay and Eva Hevia and Pryde, {David C.}",

year = "2011",

month = sep,

day = "7",

doi = "10.1016/j.tetlet.2011.06.090",

language = "English",

volume = "52",

pages = "4590--4594",

journal = "Tetrahedron Letters",

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publisher = "Elsevier Limited",

number = "36",

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Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)(2) and applications in in situ cross coupling reactions. / Blair, Victoria L.; Blakemore, David C.; Hay, Duncan et al.
In: Tetrahedron Letters, Vol. 52, No. 36, 07.09.2011, p. 4590-4594.

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

TY - JOUR

T1 - Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)(2) and applications in in situ cross coupling reactions

AU - Blair, Victoria L.

AU - Blakemore, David C.

AU - Hay, Duncan

AU - Hevia, Eva

AU - Pryde, David C.

PY - 2011/9/7

Y1 - 2011/9/7

N2 - This study investigates the ability of the mixed-metal reagent [Li(TMP)Zn(tBu)(2)] 1 to promote direct Zn-H exchange reactions (zincations) of a wide range of N-heterocyclic molecules. The generated metallated intermediates from these reactions are intercepted with I-2 and some of them are also employed as precursors in Pd-catalysed Negishi cross-coupling applications. A comparison with recent precedents in metallation chemistry reveals that for some of these heterocycles, 1 allows improved conversions, under milder conditions and in certain cases, even gives unique regioselectivities.

AB - This study investigates the ability of the mixed-metal reagent [Li(TMP)Zn(tBu)(2)] 1 to promote direct Zn-H exchange reactions (zincations) of a wide range of N-heterocyclic molecules. The generated metallated intermediates from these reactions are intercepted with I-2 and some of them are also employed as precursors in Pd-catalysed Negishi cross-coupling applications. A comparison with recent precedents in metallation chemistry reveals that for some of these heterocycles, 1 allows improved conversions, under milder conditions and in certain cases, even gives unique regioselectivities.

KW - metallation

KW - zincation

KW - N-Heterocycles

KW - lithium

KW - mixed-metal reagents

KW - directed ortho-metalation

KW - polysubstituted aromatics

KW - functionalized aromatics

KW - structual basis

KW - magnesium

KW - lithiation

KW - bases

KW - efficient

KW - diazines

KW - pyrazines

UR - http://www.scopus.com/inward/record.url?scp=79961173024&partnerID=8YFLogxK

U2 - 10.1016/j.tetlet.2011.06.090

DO - 10.1016/j.tetlet.2011.06.090

M3 - Article

SN - 0040-4039

VL - 52

SP - 4590

EP - 4594

JO - Tetrahedron Letters

JF - Tetrahedron Letters

IS - 36

ER -

Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)(2) and applications in in situ cross coupling reactions

Abstract

Keywords

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First Grant Scheme: Hybrid Magnesium-Zinc Reagents: Structural Tailoring for Synthetic and Cataltic Applications

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Alkali-metal mediated zincation of N-heterocyclic substrates using the lithium zincate complex, (THF)Li(TMP)Zn(tBu)(2) and applications in in situ cross coupling reactions

Abstract

Keywords

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Projects

First Grant Scheme: Hybrid Magnesium-Zinc Reagents: Structural Tailoring for Synthetic and Cataltic Applications

Cite this