Abstract
Ynolates are multifunctional carbanions bearing a triple bond. Due to the difficulty
in synthesizing them, their chemistry has remained relatively unexplored. However,
since the recent publication of several new methodologies for the preparation of these
interesting compounds, the versatility of ynolates in synthetic organic chemistry
has been recognized, and new aspects of ynolate chemistry, e.g., tandem reactions,
cycloadditions, olefinations of carbonyl compounds, are being developed.
1 Introduction.
2 Synthesis of Ynolates
2.1 Fragmentation of Isoxazolyl Lithium
2.2 Metalation of Silylketenes
2.3 Rearrangement of α-Keto Dianions
2.4 Oxidation of Terminal Alkynes
2.5 Flash Photolysis
2.6 Silyl Ynolates from α-Diazoacyllithium
2.7 Cleavage of Ester Dianions
2.8 Ynolate Dianions
3 Spectroscopic Analysis of Ynolates
4 Reactions of Ynolates
4.1 [2+2] Cycloaddition with Aldehydes and Ketones
4.1.1 β-Lactone Enolates
4.1.2 Tandem Reactions Leading to Multisubstituted Carbocycles
4.2 [2+2] Cycloaddition with C=N Bond
4.3 [3+2] Cycloaddition
4.3.1 Anionic Inverse Electron-Demand [3+2] Cycloaddition with Nitrones
4.3.2 Formal [3+2] Cycloaddition with Oxiranes and Aziridines
4.4 [4+2] Cycloaddition
4.5 Olefination of Carbonyl Compounds
4.5.1 Olefination of Aldehydes and Ketones
4.5.2 Stereoelectronic Effect
4.5.3 Olefination of Acylsilanes
4.5.4 Olefination of Aldimines
4.6 Reduction of Ynolates
5 Silyl Ynol Ethers
5.1 Preparation of Silyl Ynol Ethers
5.2 Reactions of Silyl Ynol Ethers
6 Conclusion
Key words
carbanions - Cycloadditions - tandem reactions - ynolates - olefination
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