From Amino Acids To Dihydrofurans: Functionalized Allenes in Modern
Organic Synthesis

Abstract

In this account, recent accomplishments in the field of target-oriented synthesis involving allenes are summarized. Allenic α-amino acid derivatives 9, which are of interest as possible vitamin B₆ decarboxylase inhibitors, were prepared by 1,6-addition of the cyano-Gilman reagent t-Bu₂CuLi·LiCN to 2-amino-substituted enynoates 8, and selective deprotection at either the amino or the ester group was realized. 2,5-Dihydrofurans 18 were obtained by cyclization of the corresponding α-hydroxyallenes; for this step, new methods (treatment with hydrogen chloride gas or acidic ion exchange resin; gold(III)-chloride catalysis) were developed. The 2-hydroxy-3,4-dienoates 14 were obtained by diastereoselective oxidation of titanium enolates formed from 3,4-dienoates 12 with di­methyl dioxirane (DMDO), whereas hydroxyallenes 16 were prepared by copper-mediated S_N2′-substitution of propargylic epoxides 15.

• 1 Introduction

• 2 Synthesis of α-Allenic α-Amino Acids

• 3 Synthesis of 2,5-Dihydrofurans

• 4 Conclusion

• 5 Experimental Section

Key words

allenes - amino acids - gold catalysis - 2,5-dihydrofurans - organocopper reagents

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25

The protonation of allenyl enolates bearing alkyl substituents at C-2 also occurs without diastereoselectivity: Krause, N. Unpublished results.

33

Without transmetalation of the lithium enolate to the less basic titanium enolate the only product obtained by treatment with the acetone soln of DMDO is the aldol adduct of the ester enolate with acetone.

35

Hoffmann-Röder, A.; Krause, N. Manuscript in preparation.