Kinetic correlation between aldehyde/enamine stereoisomers in reactions between aldehydes with [small alpha]-stereocenters and chiral pyrrolidine-based catalystsCitation formats

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Kinetic correlation between aldehyde/enamine stereoisomers in reactions between aldehydes with [small alpha]-stereocenters and chiral pyrrolidine-based catalysts. / Bures, Jordi; Armstrong, Alan; Blackmond, Donna G.

In: Chemical Science, Vol. 3, 2012, p. 1273-1277.

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@article{3dee74d7c1ce41d7b18c08da5df8999e,
title = "Kinetic correlation between aldehyde/enamine stereoisomers in reactions between aldehydes with [small alpha]-stereocenters and chiral pyrrolidine-based catalysts",
abstract = "The formation of enamines between aldehydes with [small alpha]-stereocenters and pyrrolidine-based catalysts that lack an acidic proton is examined by kinetic and spectroscopic studies. The reaction exhibits {"}kinetic stereospecificity{"} in that each enantiomer of the aldehyde initially reacts to form a specific enamine stereoisomer, prior to thermodynamic equilibration of the E and Z enamines. For the case of prolinate catalysts, each of the stereoisomeric enamines is correlated with a specific stereoisomeric oxazolidinone. The reactions of E and Z enamines with electrophiles such as DEAD lead to products of opposite stereochemistry. The product enantioselectivity observed depends on the extent to which the E and Z enamines are pre-equilibrated prior to reaction with the electrophile. General implications for selectivity in organocatalytic reactions are discussed.",
author = "Jordi Bures and Alan Armstrong and Blackmond, {Donna G.}",
note = "M1 - 4",
year = "2012",
doi = "10.1039/C2SC01082H",
language = "English",
volume = "3",
pages = "1273--1277",
journal = "Chemical Science",
issn = "2041-6520",
publisher = "Royal Society of Chemistry",

}

RIS

TY - JOUR

T1 - Kinetic correlation between aldehyde/enamine stereoisomers in reactions between aldehydes with [small alpha]-stereocenters and chiral pyrrolidine-based catalysts

AU - Bures, Jordi

AU - Armstrong, Alan

AU - Blackmond, Donna G.

N1 - M1 - 4

PY - 2012

Y1 - 2012

N2 - The formation of enamines between aldehydes with [small alpha]-stereocenters and pyrrolidine-based catalysts that lack an acidic proton is examined by kinetic and spectroscopic studies. The reaction exhibits "kinetic stereospecificity" in that each enantiomer of the aldehyde initially reacts to form a specific enamine stereoisomer, prior to thermodynamic equilibration of the E and Z enamines. For the case of prolinate catalysts, each of the stereoisomeric enamines is correlated with a specific stereoisomeric oxazolidinone. The reactions of E and Z enamines with electrophiles such as DEAD lead to products of opposite stereochemistry. The product enantioselectivity observed depends on the extent to which the E and Z enamines are pre-equilibrated prior to reaction with the electrophile. General implications for selectivity in organocatalytic reactions are discussed.

AB - The formation of enamines between aldehydes with [small alpha]-stereocenters and pyrrolidine-based catalysts that lack an acidic proton is examined by kinetic and spectroscopic studies. The reaction exhibits "kinetic stereospecificity" in that each enantiomer of the aldehyde initially reacts to form a specific enamine stereoisomer, prior to thermodynamic equilibration of the E and Z enamines. For the case of prolinate catalysts, each of the stereoisomeric enamines is correlated with a specific stereoisomeric oxazolidinone. The reactions of E and Z enamines with electrophiles such as DEAD lead to products of opposite stereochemistry. The product enantioselectivity observed depends on the extent to which the E and Z enamines are pre-equilibrated prior to reaction with the electrophile. General implications for selectivity in organocatalytic reactions are discussed.

U2 - 10.1039/C2SC01082H

DO - 10.1039/C2SC01082H

M3 - Article

VL - 3

SP - 1273

EP - 1277

JO - Chemical Science

JF - Chemical Science

SN - 2041-6520

ER -