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Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions.
J Org Chem. 2004 Dec 10; 69(25):8796-803.JO

Abstract

Levulinic acid-derived 6-diazoheptane-2,5-dione (9) serves as a common precursor in a formal synthesis of frontalin 19, and in syntheses of cis-nemorensic acid 1, 4-hydroxy-cis-nemorensic acid 2, 3-hydroxy-cis-nemorensic acid 3, and nemorensic acid 4. The key step in these syntheses is the Rh(2)(OAc)(4)-catalyzed tandem carbonyl ylide formation-intermolecular 1,3-dipolar cycloadditions of diazodione 9 with formaldehyde, alkynes or allene, which occur with high regioselectivity. Subsequent oxidative cleavage of the ring originally derived from the cyclic carbonyl ylide intermediate provides a straightforward access to polysubstituted tetrahydrofurans, and in particular an efficient entry to the nemorensic acids. Enantioselective cycloadditions with diazodione 9, using chiral rhodium catalysts, gave cycloadducts in up to 51% ee.

Authors+Show Affiliations

Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford OX1 3TA, United Kingdom. david.hodgson@chem.ox.ac.ukNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

15575760

Citation

Hodgson, David M., et al. "Stereocontrolled Syntheses of the Nemorensic Acids Using 6-diazoheptane-2,5-dione in Carbonyl Ylide Cycloadditions." The Journal of Organic Chemistry, vol. 69, no. 25, 2004, pp. 8796-803.
Hodgson DM, Le Strat F, Avery TD, et al. Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. J Org Chem. 2004;69(25):8796-803.
Hodgson, D. M., Le Strat, F., Avery, T. D., Donohue, A. C., & Brückl, T. (2004). Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. The Journal of Organic Chemistry, 69(25), 8796-803.
Hodgson DM, et al. Stereocontrolled Syntheses of the Nemorensic Acids Using 6-diazoheptane-2,5-dione in Carbonyl Ylide Cycloadditions. J Org Chem. 2004 Dec 10;69(25):8796-803. PubMed PMID: 15575760.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Stereocontrolled syntheses of the nemorensic acids using 6-diazoheptane-2,5-dione in carbonyl ylide cycloadditions. AU - Hodgson,David M, AU - Le Strat,Frédéric, AU - Avery,Thomas D, AU - Donohue,Andrew C, AU - Brückl,Tobias, PY - 2004/12/4/pubmed PY - 2005/2/16/medline PY - 2004/12/4/entrez SP - 8796 EP - 803 JF - The Journal of organic chemistry JO - J Org Chem VL - 69 IS - 25 N2 - Levulinic acid-derived 6-diazoheptane-2,5-dione (9) serves as a common precursor in a formal synthesis of frontalin 19, and in syntheses of cis-nemorensic acid 1, 4-hydroxy-cis-nemorensic acid 2, 3-hydroxy-cis-nemorensic acid 3, and nemorensic acid 4. The key step in these syntheses is the Rh(2)(OAc)(4)-catalyzed tandem carbonyl ylide formation-intermolecular 1,3-dipolar cycloadditions of diazodione 9 with formaldehyde, alkynes or allene, which occur with high regioselectivity. Subsequent oxidative cleavage of the ring originally derived from the cyclic carbonyl ylide intermediate provides a straightforward access to polysubstituted tetrahydrofurans, and in particular an efficient entry to the nemorensic acids. Enantioselective cycloadditions with diazodione 9, using chiral rhodium catalysts, gave cycloadducts in up to 51% ee. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/15575760/Stereocontrolled_syntheses_of_the_nemorensic_acids_using_6_diazoheptane_25_dione_in_carbonyl_ylide_cycloadditions_ L2 - https://doi.org/10.1021/jo048446b DB - PRIME DP - Unbound Medicine ER -