Entropy-Controlled Asymmetric Synthesis. How Differential Activation Entropy Is Induced in Chiral Tethered Reactions

Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to...

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Bibliographic Details
Published inOrganic letters Vol. 3; no. 1; pp. 37 - 40
Main Authors Sugimura, Takashi, Hagiya, Kazutake, Sato, Yasuhiro, Tei, Takahiro, Tai, Akira, Okuyama, Tadashi
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 11.01.2001
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
METAL CARBENE TRANSFORMATIONS
OXIDATION
LINKING BRIDGE
DIAZO ESTER
INSERTION
2,4-PENTANEDIOL TETHER
ENOL ETHER
CYCLOPROPANATION
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Summary:Kinetic measurements to determine effective molarities of intramolecular reactions using 2,4-pentanediol and related tethers showed that methyl groups on the tether accelerate the major diastereomeric process but decelerate the minor process. The efficient promotion of stereocontrol is suggested to be due to chiral perturbation of the reaction rate through the entropy term. The conformation of the encounter complex of the reagent and reactant moieties was deduced by stereochemical analysis of the intramolecular adducts.
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ISSN:1523-7060
1523-7052
DOI:10.1021/ol006741m