Expanding the Utility of Lithiated Epoxides and Aziridines in Synthesis

Abstract

This account details new reactions and synthetic uses of lithiated epoxides and aziridines that have been developed in the principal author’s laboratories.

• 1 Introduction

• 2 Epoxides and Organolithiums

• 2.1 Enantioselective Desymmetrisation of meso-Epoxides by α-Lithiation-Rearrangement

• 2.2 Reductive Alkylation of Epoxides with Organolithiums

• 2.3 α-Lithiated Epoxides of Cycloalkenes as Nucleophiles

• 2.4 α-Lithiated Terminal Epoxides as Nucleophiles

• 3 Terminal Epoxides and Lithium Amides

• 3.1 Electrophile Trapping

• 3.2 Enamines from Epoxides and Hindered Lithium Amides

• 3.3 Intramolecular Cyclopropanation

• 3.4 Reductive Alkylation in the presence of LTMP

• 3.5 Dimerisation of α-Lithiated Epoxides

• 4 α-Lithiated Aziridines

• 4.1 Reductive Alkylation of Aziridines with Organolithiums

• 4.2 α-Lithiated Terminal Aziridines as Nucleophiles

• 5 Summary and Outlook

Key words

asymmetric synthesis - aziridines - carbenoids - epoxides - lithiation

References and Notes

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1

Present address: School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD, UK.

17

For our preparation of i-PrLi see http://www.syntheticpages.org/search.php?&action = 1&page = 1&id = 195.

46

The trans-stereochemistry was anticipated based on the reductive alkylation studies of Mioskowski and co-workers; see ref. 35.