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

33 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",

issn = "0040-4039",

publisher = "Elsevier Limited",

number = "36",

}

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 - https://www.scopus.com/pages/publications/79961173024

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