A combined DFT and NMR investigation of the zinc organometallic intermediate proposed in the syn-selective tandem chain extension-aldol reaction of β-keto esters

Aiken, Karelle S., Eger, Wilhelm A., Williams, Craig M., Spencer, Carley M. and Zercher, Charles K. (2012) A combined DFT and NMR investigation of the zinc organometallic intermediate proposed in the syn-selective tandem chain extension-aldol reaction of β-keto esters. Journal of Organic Chemistry, 77 14: 5942-5955.


Author Aiken, Karelle S.
Eger, Wilhelm A.
Williams, Craig M.
Spencer, Carley M.
Zercher, Charles K.
Title A combined DFT and NMR investigation of the zinc organometallic intermediate proposed in the syn-selective tandem chain extension-aldol reaction of β-keto esters
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2012-07
Sub-type Article (original research)
DOI 10.1021/jo3004925
Volume 77
Issue 14
Start page 5942
End page 5955
Total pages 14
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2013
Language eng
Abstract The tandem chain extension-aldol (TCA) reaction of β-keto esters provides an α-substituted γ-keto ester with an average syn:anti selectivity of 10:1. It is proposed that the reaction proceeds via a carbon-zinc bound organometallic intermediate potentially bearing mechanistic similarity to the Reformatsky reaction. Evidence, derived from control Reformatsky reactions and a study of the structure of the TCA intermediate utilizing DFT methods and NMR spectroscopy, suggests the γ-keto group of the TCA intermediate plays a significant role in diastereoselectivity observed in this reaction. Such coordination effects have design implications for future zinc mediated reactions.
Keyword Gaussian-basis sets
Ketomethylene isosteres
Molecular calculations
Density functionals
3rd-row atoms
Vibsanin-E
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2013 Collection
School of Chemistry and Molecular Biosciences
 
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