Structure of the Mixed Aggregates between a Chiral Lithium Amide and Phenyllithium or Vinyllithium

Hassan Oulyadi; Catherine Fressigné; Yi Yuan; Jacques Maddaluno; Anne Harrison-Marchand

doi:10.1021/om300352p

Structure of the Mixed Aggregates between a Chiral Lithium Amide and Phenyllithium or Vinyllithium

Organometallics ◽

10.1021/om300352p ◽

2012 ◽

Vol 31 (13) ◽

pp. 4801-4809 ◽

Cited By ~ 17

Author(s):

Hassan Oulyadi ◽

Catherine Fressigné ◽

Yi Yuan ◽

Jacques Maddaluno ◽

Anne Harrison-Marchand

Keyword(s):

Lithium Amide ◽

Mixed Aggregates

Mixed Aggregates: Lithium Enolate of 3-Pentanone and a Chiral Lithium Amide

Journal of the American Chemical Society ◽

10.1021/ja001372a ◽

2000 ◽

Vol 122 (32) ◽

pp. 7829-7830 ◽

Cited By ~ 32

Author(s):

Chengzao Sun ◽

Paul G. Williard

Keyword(s):

Lithium Amide ◽

Lithium Enolate ◽

Mixed Aggregates

Mixed Aggregates Containingn-Butyl-,sec-Butyl-, ortert-Butyllithium and a Chiral Lithium Amide Derived fromN-Isopropyl-O-methyl Valinol

Journal of the American Chemical Society ◽

10.1021/ja972277d ◽

1997 ◽

Vol 119 (48) ◽

pp. 11693-11694 ◽

Cited By ~ 46

Author(s):

Paul G. Williard ◽

Chengzao Sun

Keyword(s):

Lithium Amide ◽

Mixed Aggregates

Probing solvent effects on mixed aggregates associating a chiral lithium amide and n-BuLi by NMR: from structure to reactivity

Dalton Transactions ◽

10.1039/c4dt01156b ◽

2014 ◽

Vol 43 (38) ◽

pp. 14219-14228 ◽

Cited By ~ 8

Author(s):

Gabriella Barozzino-Consiglio ◽

Mathieu Rouen ◽

Hassan Oulyadi ◽

Anne Harrison-Marchand ◽

Jacques Maddaluno

Keyword(s):

Solvent Effects ◽

Test Reaction ◽

Lithium Amide ◽

Mixed Aggregates

NMR shows a direct correlation between the concentration of a chiral lithium amide/n-BuLi complex and ees of a test reaction.

Ab Initio MO Calculations of NMR15N–6Li Coupling Constants in Lithium Amide Monomers, Oligomers, and Mixed Aggregates with LiCl

Bulletin of the Chemical Society of Japan ◽

10.1246/bcsj.69.305 ◽

1996 ◽

Vol 69 (2) ◽

pp. 305-309 ◽

Cited By ~ 17

Author(s):

Terutake Koizumi ◽

Kenji Morihashi ◽

Osamu Kikuchi

Keyword(s):

Ab Initio ◽

Coupling Constants ◽

Mo Calculations ◽

Lithium Amide ◽

Ab Initio Mo Calculations ◽

Mixed Aggregates ◽

Ab Initio Mo

Mixed Aggregates of an Alkyl Lithium Reagent and a Chiral Lithium Amide Derived from N-Ethyl-O-triisopropylsilyl Valinol

Journal of the American Chemical Society ◽

10.1021/ja406912h ◽

2013 ◽

Vol 135 (38) ◽

pp. 14367-14379 ◽

Cited By ~ 23

Author(s):

Chicheung Su ◽

Russell Hopson ◽

Paul G. Williard

Keyword(s):

Lithium Amide ◽

Mixed Aggregates

Mixed aggregates: crystal structures of a lithium ketone enolate/lithium amide and of a sodium ester enolate/sodium amide

Journal of the American Chemical Society ◽

10.1021/ja00179a066 ◽

1990 ◽

Vol 112 (23) ◽

pp. 8602-8604 ◽

Cited By ~ 44

Author(s):

Paul G. Williard ◽

Mark J. Hintze

Keyword(s):

Crystal Structures ◽

Lithium Amide ◽

Mixed Aggregates ◽

Ester Enolate ◽

Sodium Amide

Mixed Aggregates of Organolithium Compounds

Mini-Reviews in Organic Chemistry ◽

10.2174/1570193043488863 ◽

2004 ◽

Vol 1 (2) ◽

pp. 209-217 ◽

Cited By ~ 20

Author(s):

Lawrence Pratt

Keyword(s):

Organolithium Compounds ◽

Mixed Aggregates

Lithium-mediated Ferration of Fluoroarenes

CHIMIA International Journal for Chemistry ◽

10.2533/chimia.2020.866 ◽

2020 ◽

Vol 74 (11) ◽

pp. 866-870

Author(s):

Lewis C. H. Maddock ◽

Alan Kennedy ◽

Eva Hevia

Keyword(s):

Hydrogen Atom ◽

Organometallic Chemistry ◽

Room Temperature ◽

Structural Elucidation ◽

Side Reactions ◽

Metal Base ◽

Lithium Amide ◽

Mixed Metal ◽

Important Challenge

While fluoroaryl fragments are ubiquitous in many pharmaceuticals, the deprotonation of fluoroarenes using organolithium bases constitutes an important challenge in polar organometallic chemistry. This has been widely attributed to the low stability of the in situ generated aryl lithium intermediates that even at –78 °C can undergo unwanted side reactions. Herein, pairing lithium amide LiHMDS (HMDS = N{SiMe3}2) with FeII(HMDS)2 enables the selective deprotonation at room temperature of pentafluorobenzene and 1,3,5-trifluorobenzene via the mixed-metal base [(dioxane)LiFe(HMDS)3] (1) (dioxane = 1,4-dioxane). Structural elucidation of the organometallic intermediates [(dioxane)Li(HMDS)2Fe(ArF)] (ArF = C6F5, 2; 1,3,5-F3-C6H2, 3) prior electrophilic interception demonstrates that these deprotonations are actually ferrations, with Fe occupying the position previously filled by a hydrogen atom. Notwithstanding, the presence of lithium is essential for the reactions to take place as Fe II (HMDS)2 on its own is completely inert towards the metallation of these substrates. Interestingly 2 and 3 are thermally stable and they do not undergo benzyne formation via LiF elimination.

The Metalation and Addition Reactions of Allylbenzene and Propenylbenzene with Butyllithium and Lithium Amide

Journal of the American Chemical Society ◽

10.1021/ja01578a060 ◽

1957 ◽

Vol 79 (21) ◽

pp. 5809-5814 ◽

Cited By ~ 20

Author(s):

Harry F. Herbrandson ◽

David S. Mooney

Keyword(s):

Addition Reactions ◽

Lithium Amide

Compositional flexibility in Li-N-H materials: implications for ammonia catalysis and hydrogen storage.

Physical Chemistry Chemical Physics ◽

10.1039/d1cp02440j ◽

2021 ◽

Author(s):

Joshua Makepeace ◽

Jake M Brittain ◽

Alisha Sukhwani Manghnani ◽

Claire Murray ◽

Thomas J Wood ◽

...

Keyword(s):

Energy Storage ◽

Hydrogen Storage ◽

Compositional Variation ◽

Lithium Amide ◽

Lithium Imide ◽

Energy Storage Applications

Li-N-H materials, particularly lithium amide and lithium imide, have been explored for use in a variety of energy storage applications in recent years. Compositional variation within the parent lithium imide,...