A Stable Methyl Phosphane Oxide/Lithium Amide Complex: a Structural and MO Calculational Investigation of the Mechanism of Proton Abstraction by Alkali Metal Reagents†
- 20 September 1996
- journal article
- research article
- Published by Wiley in Angewandte Chemie International Edition in English
- Vol. 35 (17) , 1942-1944
- https://doi.org/10.1002/anie.199619421
Abstract
The initiation step in a deprotonation of CH‐acidic compounds could be the formation of a complex between the organic precursor and the metalation reagent. This is the conclusion drawn from the reaction of Ph2P(O)CH3 with (Me3Si)2NLi, which yielded a stable dimeric adduct [(Me3Si)2NLi·OP(CH3)Ph2]2 with a central Li2N2 ring. MO calculations on the model system H2LiNLi·OP(CH3)2 support these experimental findings.Keywords
This publication has 32 references indexed in Scilit:
- Stereokontrolle in der organischen Synthese durch Verwendung der DiphenylphosphorylgruppeAngewandte Chemie, 1996
- Ireland-Claisen rearrangements of enediyne lactones: tandem Claisen-Bergman strategy for stereocontrolled tetrahydronaphthalene synthesisJournal of the American Chemical Society, 1993
- Chemistry of organosilicon compounds. 297. Lithium pentakis(dimethylsilyl)cyclopentadienide and formation of isolable coordination complexes with ketones: [(R2C:O)Li.{C5(SiMe2H)5}]Journal of the American Chemical Society, 1993
- [Lithiumpiperidid‐Piperidin]4: Kristallstruktur eines oligomeren Lithiumamid‐Amin‐Komplexes, einer Zwischenstufe bei der Lithiierung von AminenAngewandte Chemie, 1992
- Struktur des neuartigen, zweifach Ketimin‐komplexierten Natriumketimids [(tBu2CNNa)4(HNCtBu2)2] im Kristall und in Lösung: Die Stapelung komplexierter und nicht komplexierter (NNa)2‐Ringe zu einem stark verzerrten (NNa)4‐CubanAngewandte Chemie, 1992
- Characterization of complexes between esters and lithium hexamethyldisilazideJournal of the American Chemical Society, 1992
- Modell eines solvens‐verbrückten Ionenpaares mit N-H ⃛C‐Wasserstoffbrücken zwischen Amin und Carbanion – Kristallstruktur von [Fluorenyllithium·2Ethylendiamin]∞Angewandte Chemie, 1989
- Applications of the stereochemically-controlled Horner-Wittig reaction: synthesis of feniculin, (E)-non-6-en-1-ol, a pheromone of the mediterranean fruit fly, (E)- and (Z)-dec-5-en-1-ol, tri-substituted alkenes, and (Z)-α-bisaboleneJournal of the Chemical Society, Perkin Transactions 1, 1987
- The stereocontrolled Horner-Wittig reaction: synthesis of disubstituted alkenesJournal of the Chemical Society, Perkin Transactions 1, 1985
- The isolation and crystal structure of [Ph(2-Pyr)NLi]·(HMPA)·[Ph(2-Pyr)NH]; a model monomeric orgenonitrogen–lithium species containing co-ordination of lithium by both an anchimeric pyridyl N-atom and by a potentially reactive amine ligandJournal of the Chemical Society, Chemical Communications, 1984