Abstract
The chemistry and synthetic utility of α-lithiated haloalkyloxazolines, oxazolinyl epoxides, and aziridines are highlighted in this account. These lithiated species, which are easily generated, can be captured by electrophiles to give more functionalized derivatives. Spectroscopic and computational studies have proved useful, not only in relation to understanding the chemistry of lithiated species in general, but also in the elucidation of the mechanisms of their lithiation and the stereochemistry of their reactions. The combination of bench experiments with spectroscopic investigations and density functional theory calculations has contributed enormously to increasing the synthetic potential of the lithiated oxazolines that are described in this account.
1 Introduction
2 Lithiation and Reactions of 2-(Haloalkyl)oxazolines and Their Applications
2.1 Synthesis of Oxazolinyl and Formyl Epoxides
2.2 Synthesis of Oxazolinylcyclopropanes
2.3 Synthesis of Oxazolinyl Estrones
2.4 Synthesis of Alkenyl Oxazolines and Oxazolinyl Oxazetidines
2.5 Synthesis of Oxazolinyl Aziridines
2.6 Vicarious Nucleophilic Substitution Reactions of (Chloroalkyl)oxazolines: Synthesis of (Nitrobenzyl)oxazolines and Dinitrophenyl(dioxazolinyl)ethenes
3 Lithiated Oxazolinyloxiranes: Generation and Reactions
3.1 Generation and Reactions of α-Lithiated Oxazolinyloxiranes
3.2 Synthesis of Oxazolinylaryl Alkanones
3.3 Synthesis of Allylic Alcohols from Oxazolinyloxiranes
3.4 Isomerization of Oxazolinyl Allylic Alcohols: Synthesis of 3-Alkylidene-2-iminooxetanes
3.5 Reactions of Lithiated Oxazolinyloxiranes with Nitrones: Synthesis of α-Epoxy γ-Amino Acids
3.6 Reactions of Lithiated Oxazolinyloxiranes with α,β-Unsaturated Fischer Carbene Complexes: Synthesis of Cyclopropyl-Fused γ-Butyrolactones
3.7 On the Stereochemistry of α-Lithiated Oxazolinyloxiranes
3.8 Synthesis of Optically Active ortho -Sulfinylphenyl Oxazolinyl Epoxy Alcohols
3.9 α-Lithiated Benzothiazolyloxiranes
3.10 α-Lithiated Benzotriazolyloxiranes
3.11 Synthesis of α,β–Epoxy-γ-butyrolactones from β-Lithiated Oxazolinyloxiranes
3.12 Synthesis of α,β-Epoxy-γ-amino acids and α,β-Epoxy-γ-butyrolactams
3.13 Synthesis of Polysubstituted Oxazolinyl Cyclopropanes
3.14 Lithiation Of Terminal Oxazolinyloxirane: Synthesis of Trisubstituted Oxazolinyloxiranes and an (E )-1,4-Dioxazolinyl-1,4-diphenylbut-2-ene-1,4-diol
4 Lithiated Oxazolinyl Aziridines
4.1 α-Lithiated N-Alkyl(aryl)oxazolinylaziridines: Synthesis of Aziridinolactones
4.2 Lithiation of N -Alkyl Terminal Aziridines
4.3 Lithiation of Heterosubstituted Oxazolinylaziridines
4.4 Lithiation of N -Sulfonyl- and N -Phosphinylaziridines
5 Concluding Remarks
Key words epoxides - asymmetric synthesis - heterocycles - lithiation - lactones - lactams
