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Synthesis 2002(12): 1625-1642
DOI: 10.1055/s-2002-33635
DOI: 10.1055/s-2002-33635
REVIEW
© Georg Thieme Verlag Stuttgart · New York
Recent Developments in the Chemistry of Lithiated Epoxides
Further Information
Received
17 June 2002
Publication Date:
05 September 2002 (online)
Publication History
Publication Date:
05 September 2002 (online)
Abstract
Although the lithium base-induced β-elimination of epoxides to allylic alcohols is a well-known reaction, α-lithiation has also been described many times. The resulting lithiated epoxides, first postulated as intermediates by Cope in 1951, have been invoked in a wide range of reactions, with their carbenoid properties allowing for very different reactivities. This review covers the recent advances (˜1996 - mid 2002) in the rich chemistry of these main-group metal carbenoids, especially their generation by enantioselective α-deprotonation.
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1 Introduction
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2 Carbenoid Chemistry of Lithiated Epoxides: C-H Insertion and 1,2-Shifts
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2.1 Transannular C-H Insertion
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2.2 Transannular Rearrangement versus 1,2-Shift of Hydrogen
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2.3 1,2-Shifts
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2.4 Cyclopropanations
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3 Carbenoid Chemitry of Lithiated Epoxides: Reductive Alkylation
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3.1 Olefin Formation: Allylic Alcohols via Reductive Alkylation
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3.2 Olefin Formation versus C-H Insertion
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3.3 Olefin Formation versus Electrophile Trapping
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4 Electrophile Trapping of Lithiated Epoxides
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4.1 Lithiated Epoxides Bearing Anion Stabilising Groups
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4.1.1 Transmetallation of Stabilised Lithiated Epoxides
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4.1.2 Sulfonyl-stabilised Lithiated Epoxides
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4.1.3 Carbonyl-stabilised Lithiated Epoxides
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4.1.4 Oxazolinyl-stabilised Lithiated Epoxides
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4.1.5 Imine-substituted Lithiated Epoxides
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4.1.6 Trifluoromethyl-substituted Lithiated Epoxides
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4.1.7 Silyl-stabilised Lithiated Epoxides in Synthesis
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4.1.8 Phenyl-stabilised Lithiated Epoxide
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4.2 ‘Remote’ Stabilisation of a Lithiated Epoxide
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4.3 Generation of Non-stabilised and Destabilised Lithiated Epoxides
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4.3.1 Desulfinylation of Sulfinyloxiranes
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4.3.2 Deprotonation of ‘Simple’ Epoxides
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5 Concluding Remarks
Key words
asymmetric synthesis - carbanions - carbenoids - epoxides - rearrangements
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