Structural and synthetic insights into pyridine homocouplings mediated by a β-diketiminato magnesium amide complex

Eva Hevia, Ross McLellan, Laia Davin, William Clegg, Alan Kennedy, Michael R Probert

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Reaction of [(DippNacnac)Mg(TMP)] (1) with 4‐subtituted pyridines proceeds via sequential regioselective metalation and 1,2‐addition to furnish a range of symmetric 4,4'R2‐2,2'‐bipyridines in good yield, representing a new entry into bipyridine synthesis. Interestingly, the reaction with of 1 with 2‐OMe‐pyridine led to formation of asymmetric bipyridine 6, resulting from the C6‐magnesiation of the heterocycle followed by a C‐C coupling step by addition to the C2 position of a second, non‐metallated molecule, and subsequent elimination of [DippNacnacMgOMe]2 (7). Synthesis combined with spectroscopic and structural analysis help rationalise the underlying processes resulting in the observed reactivity, and elucidates the key role of the sterically encumbered β‐diketiminate ligand plays in determining regioselectivity.
LanguageEnglish
Number of pages7
JournalChemistry - A European Journal
Early online date27 Jul 2018
DOIs
Publication statusE-pub ahead of print - 27 Jul 2018

Fingerprint

Amides
Magnesium
Thymidine Monophosphate
Pyridines
Regioselectivity
2,2'-Dipyridyl
Spectroscopic analysis
Structural analysis
Ligands
Molecules
pyridine

Keywords

  • bipyridine synthesis
  • B-diketiminate ligand
  • spetroscopic and structural analysis

Cite this

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title = "Structural and synthetic insights into pyridine homocouplings mediated by a β-diketiminato magnesium amide complex",
abstract = "Reaction of [(DippNacnac)Mg(TMP)] (1) with 4‐subtituted pyridines proceeds via sequential regioselective metalation and 1,2‐addition to furnish a range of symmetric 4,4'R2‐2,2'‐bipyridines in good yield, representing a new entry into bipyridine synthesis. Interestingly, the reaction with of 1 with 2‐OMe‐pyridine led to formation of asymmetric bipyridine 6, resulting from the C6‐magnesiation of the heterocycle followed by a C‐C coupling step by addition to the C2 position of a second, non‐metallated molecule, and subsequent elimination of [DippNacnacMgOMe]2 (7). Synthesis combined with spectroscopic and structural analysis help rationalise the underlying processes resulting in the observed reactivity, and elucidates the key role of the sterically encumbered β‐diketiminate ligand plays in determining regioselectivity.",
keywords = "bipyridine synthesis, B-diketiminate ligand, spetroscopic and structural analysis",
author = "Eva Hevia and Ross McLellan and Laia Davin and William Clegg and Alan Kennedy and Probert, {Michael R}",
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doi = "10.1002/chem.201803297",
language = "English",
journal = "Chemistry - A European Journal",
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TY - JOUR

T1 - Structural and synthetic insights into pyridine homocouplings mediated by a β-diketiminato magnesium amide complex

AU - Hevia, Eva

AU - McLellan, Ross

AU - Davin, Laia

AU - Clegg, William

AU - Kennedy, Alan

AU - Probert, Michael R

PY - 2018/7/27

Y1 - 2018/7/27

N2 - Reaction of [(DippNacnac)Mg(TMP)] (1) with 4‐subtituted pyridines proceeds via sequential regioselective metalation and 1,2‐addition to furnish a range of symmetric 4,4'R2‐2,2'‐bipyridines in good yield, representing a new entry into bipyridine synthesis. Interestingly, the reaction with of 1 with 2‐OMe‐pyridine led to formation of asymmetric bipyridine 6, resulting from the C6‐magnesiation of the heterocycle followed by a C‐C coupling step by addition to the C2 position of a second, non‐metallated molecule, and subsequent elimination of [DippNacnacMgOMe]2 (7). Synthesis combined with spectroscopic and structural analysis help rationalise the underlying processes resulting in the observed reactivity, and elucidates the key role of the sterically encumbered β‐diketiminate ligand plays in determining regioselectivity.

AB - Reaction of [(DippNacnac)Mg(TMP)] (1) with 4‐subtituted pyridines proceeds via sequential regioselective metalation and 1,2‐addition to furnish a range of symmetric 4,4'R2‐2,2'‐bipyridines in good yield, representing a new entry into bipyridine synthesis. Interestingly, the reaction with of 1 with 2‐OMe‐pyridine led to formation of asymmetric bipyridine 6, resulting from the C6‐magnesiation of the heterocycle followed by a C‐C coupling step by addition to the C2 position of a second, non‐metallated molecule, and subsequent elimination of [DippNacnacMgOMe]2 (7). Synthesis combined with spectroscopic and structural analysis help rationalise the underlying processes resulting in the observed reactivity, and elucidates the key role of the sterically encumbered β‐diketiminate ligand plays in determining regioselectivity.

KW - bipyridine synthesis

KW - B-diketiminate ligand

KW - spetroscopic and structural analysis

UR - https://onlinelibrary.wiley.com/journal/15213765

U2 - 10.1002/chem.201803297

DO - 10.1002/chem.201803297

M3 - Article

JO - Chemistry - A European Journal

T2 - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

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