Control of regioselectivity and stereoselectivity in (4 + 3) cycloadditions of chiral oxyallyls with unsymmetrically disubstituted furans

Du, Yunfei, Krenske, Elizabeth H., Antoline, Jennifer E., Lohse, Andrew G., Houk, K. N. and Hsung, Richard P. (2013) Control of regioselectivity and stereoselectivity in (4 + 3) cycloadditions of chiral oxyallyls with unsymmetrically disubstituted furans. Journal of Organic Chemistry, 78 5: 1753-1759. doi:10.1021/jo3011792


Author Du, Yunfei
Krenske, Elizabeth H.
Antoline, Jennifer E.
Lohse, Andrew G.
Houk, K. N.
Hsung, Richard P.
Title Control of regioselectivity and stereoselectivity in (4 + 3) cycloadditions of chiral oxyallyls with unsymmetrically disubstituted furans
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2013-03
Sub-type Article (original research)
DOI 10.1021/jo3011792
Volume 78
Issue 5
Start page 1753
End page 1759
Total pages 7
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2014
Language eng
Abstract The regioselectivities and stereoselectivities of ZnCl2- catalyzed (4 + 3) cycloadditions between chiral oxazolidinone-substituted oxyallyls and unsymmetrical disubstituted furans have been determined. The substitution pattern on the furan is found to provide a valuable tool for controlling the stereochemistry (endo-I or endo-II) of the 7-membered cycloadduct. While cycloadditions with monosubstituted furans usually favor endo-I products, from addition of the furan to the more crowded face of the oxyallyl, cycloadditions with 2,3- and 2,5-disubstituted furans instead favor the endo-II stereochemistry. Density functional theory calculations are performed to account for the selectivities. For monosubstituted furans, the crowded transition state leading to the endo-I cycloadduct is stabilized by an edge-to-face interaction between the furan and the oxazolidinone 4-Ph group, but this stabilization is overcome by steric clashing if the furan bears a 2-CO2R group or is 2,3-disubstituted.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Non HERDC
School of Chemistry and Molecular Biosciences
 
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Created: Mon, 13 May 2013, 16:40:32 EST by Elizabeth Krenske on behalf of School of Chemistry & Molecular Biosciences