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Evans Enolates: The Influence Of Aggregation And Solvation On The Mechanism Of The Aldol Addition To Lithiated Oxazolidinone-Derived Enolates

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The results of a combination of 6Li and 13C NMR spectroscopic and computational studies of oxazolidinone-based lithium enolates-Evans enolates-in tetrahydrofuran (THF) solution revealed a mixture of dimers, tetramers, and oligomers (possibly ladders). The distribution depended on the structure of the oxazolidinone auxiliary, substituent on the enolate, and THF concentration (in THF/toluene mixtures). The unsolvated tetrameric form contained a D2d-symmetric core structure, whereas the dimers were determined experimentally and computationally to be trisolvates with several isomeric forms. Aldol additions to isobutyraldehyde and cyclohexanone with lithium enolates derived from Evans enolates are described. The trisolvated dimeric enolates undergo rapid addition to isobutyraldehyde to give a 12:1 syn:syn selectivity in high yield along with small amounts of one anti isomer. The efficacy of the addition depends critically on aging effects and the reaction quench. Unsolvated tetrameric enolates that form on warming the solutions are unreactive toward isobutyraldehyde and undergo retroaldol reaction under forcing conditions. Additions to cyclohexanone are relatively slow but form a ! single isomeric adduct in >80% yield. The ketone-derived aldolates are robust. All attempts to control stereoselectivity by controlling aggregation failed. Rate studies of addition to cyclohexanone trace the lack of aggregation-dependent selectivities to a monomer-based mechanism. The synthetic implications and possible utility of lithium enolates in Evans aldol additions are discussed. !

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2015-08-17

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Evans Enolates; oxazolidinone; aldol

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Collum,David B

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Coates,Geoffrey
Dichtel,William Robert

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Chemistry and Chemical Biology

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Ph. D., Chemistry and Chemical Biology

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Doctor of Philosophy

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dissertation or thesis

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