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Rhodium(I)-catalyzed nucleophilic ring-opening reactions of oxabicyclo adducts derived from the [4 + 2]-cycloaddition of 2-imido-substituted furans.

Publication ,  Journal Article
Padwa, A; Wang, Q
Published in: The Journal of organic chemistry
April 2006

A series of 2-imido-substituted furans containing tethered unsaturation were prepared by the addition of the lithium carbamate of furan-2-ylcarbamic acid tert-butyl ester to a solution of the mixed anhydride of an appropriately substituted 3-butenoic acid. The initially formed imido furans undergo a rapid intramolecular [4 + 2]-cycloaddition at room temperature to deliver the Diels-Alder cycloadducts in good to excellent yield. Isolation of the highly labile oxabicyclic adduct is believed to be a consequence of the lower reaction temperatures employed as well as the presence of the extra carbonyl group, which diminishes the basicity of the nitrogen atom, thereby retarding the ring cleavage/rearrangement reaction generally encountered with related systems. By using a Rh(I)-catalyzed ring opening of the oxabicyclic adduct with various nucleophilic reagents, it was possible to prepare highly functionalized hexahydro-1H-indol-2(3H)-one derivatives in good yield. The major stereoisomer obtained possesses a cis-relationship between the nucleophile and hydroxyl group in the ring-opened product. The stereochemistry was unequivocally established by X-ray crystallographic analysis. Coordination of Rh(I) to the alkenyl pi-bond followed by a nitrogen-assisted cleavage of the carbon-oxygen bond occurs to furnish a pi-allyl rhodium(III) species. Addition of the nucleophile then occurs from the least hindered terminus of the resulting pi-allyl rhodium(III) complex. Proton exchange followed by rhodium(I) decomplexation ultimately leads to the cis-diastereomer.

Duke Scholars

Published In

The Journal of organic chemistry

DOI

EISSN

1520-6904

ISSN

0022-3263

Publication Date

April 2006

Volume

71

Issue

8

Start / End Page

3210 / 3220

Related Subject Headings

  • Rhodium
  • Organic Chemistry
  • Molecular Structure
  • Imides
  • Heterocyclic Compounds, 2-Ring
  • Furans
  • Catalysis
  • Carbamates
  • Aza Compounds
  • 0305 Organic Chemistry
 

Citation

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Padwa, A., & Wang, Q. (2006). Rhodium(I)-catalyzed nucleophilic ring-opening reactions of oxabicyclo adducts derived from the [4 + 2]-cycloaddition of 2-imido-substituted furans. The Journal of Organic Chemistry, 71(8), 3210–3220. https://doi.org/10.1021/jo060238r
Padwa, Albert, and Qiu Wang. “Rhodium(I)-catalyzed nucleophilic ring-opening reactions of oxabicyclo adducts derived from the [4 + 2]-cycloaddition of 2-imido-substituted furans.The Journal of Organic Chemistry 71, no. 8 (April 2006): 3210–20. https://doi.org/10.1021/jo060238r.
Padwa, Albert, and Qiu Wang. “Rhodium(I)-catalyzed nucleophilic ring-opening reactions of oxabicyclo adducts derived from the [4 + 2]-cycloaddition of 2-imido-substituted furans.The Journal of Organic Chemistry, vol. 71, no. 8, Apr. 2006, pp. 3210–20. Epmc, doi:10.1021/jo060238r.
Journal cover image

Published In

The Journal of organic chemistry

DOI

EISSN

1520-6904

ISSN

0022-3263

Publication Date

April 2006

Volume

71

Issue

8

Start / End Page

3210 / 3220

Related Subject Headings

  • Rhodium
  • Organic Chemistry
  • Molecular Structure
  • Imides
  • Heterocyclic Compounds, 2-Ring
  • Furans
  • Catalysis
  • Carbamates
  • Aza Compounds
  • 0305 Organic Chemistry