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Catalytic enantioselective intermolecular cycloadditions of 2-diazo-3,6-diketoester-derived carbonyl ylides with alkene dipolarophiles.
Proc Natl Acad Sci U S A. 2004 Apr 13; 101(15):5450-4.PN

Abstract

Catalyzed cascade reactions that generate molecular complexity rapidly and in an enantioselective manner are attractive methods for asymmetric synthesis. In the present article, chiral rhodium catalysts are shown to effect such a transformation by using a range of 2-diazo-3,6-diketoesters with bicyclo[2.2.1]alkenes and styrenes as reaction partners. The reactions are likely to proceed by formation of a catalyst-complexed carbonyl ylide from the diazo compound, followed by intermolecular cycloaddition with the alkene dipolarophile. It was possible to obtain high levels of asymmetric induction [up to 89% enantiomeric excess (ee) and 92% ee for the two chiral catalysts investigated]. Enantioselectivity is not highly sensitive to substituent variation at the ketone that forms the ylide; however, branching does improve ee. Observations of dipolarophile-dependent enantiofacial selectivity in the cycloadditions indicate that the dipolarophile can be intimately involved in the enantiodiscrimination process.

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 availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

15037752

Citation

Hodgson, David M., et al. "Catalytic Enantioselective Intermolecular Cycloadditions of 2-diazo-3,6-diketoester-derived Carbonyl Ylides With Alkene Dipolarophiles." Proceedings of the National Academy of Sciences of the United States of America, vol. 101, no. 15, 2004, pp. 5450-4.
Hodgson DM, Brückl T, Glen R, et al. Catalytic enantioselective intermolecular cycloadditions of 2-diazo-3,6-diketoester-derived carbonyl ylides with alkene dipolarophiles. Proc Natl Acad Sci U S A. 2004;101(15):5450-4.
Hodgson, D. M., Brückl, T., Glen, R., Labande, A. H., Selden, D. A., Dossetter, A. G., & Redgrave, A. J. (2004). Catalytic enantioselective intermolecular cycloadditions of 2-diazo-3,6-diketoester-derived carbonyl ylides with alkene dipolarophiles. Proceedings of the National Academy of Sciences of the United States of America, 101(15), 5450-4.
Hodgson DM, et al. Catalytic Enantioselective Intermolecular Cycloadditions of 2-diazo-3,6-diketoester-derived Carbonyl Ylides With Alkene Dipolarophiles. Proc Natl Acad Sci U S A. 2004 Apr 13;101(15):5450-4. PubMed PMID: 15037752.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Catalytic enantioselective intermolecular cycloadditions of 2-diazo-3,6-diketoester-derived carbonyl ylides with alkene dipolarophiles. AU - Hodgson,David M, AU - Brückl,Tobias, AU - Glen,Rebecca, AU - Labande,Agnès H, AU - Selden,Deborah A, AU - Dossetter,Alexander G, AU - Redgrave,Alison J, Y1 - 2004/03/22/ PY - 2004/3/24/pubmed PY - 2004/3/24/medline PY - 2004/3/24/entrez SP - 5450 EP - 4 JF - Proceedings of the National Academy of Sciences of the United States of America JO - Proc Natl Acad Sci U S A VL - 101 IS - 15 N2 - Catalyzed cascade reactions that generate molecular complexity rapidly and in an enantioselective manner are attractive methods for asymmetric synthesis. In the present article, chiral rhodium catalysts are shown to effect such a transformation by using a range of 2-diazo-3,6-diketoesters with bicyclo[2.2.1]alkenes and styrenes as reaction partners. The reactions are likely to proceed by formation of a catalyst-complexed carbonyl ylide from the diazo compound, followed by intermolecular cycloaddition with the alkene dipolarophile. It was possible to obtain high levels of asymmetric induction [up to 89% enantiomeric excess (ee) and 92% ee for the two chiral catalysts investigated]. Enantioselectivity is not highly sensitive to substituent variation at the ketone that forms the ylide; however, branching does improve ee. Observations of dipolarophile-dependent enantiofacial selectivity in the cycloadditions indicate that the dipolarophile can be intimately involved in the enantiodiscrimination process. SN - 0027-8424 UR - https://www.unboundmedicine.com/medline/citation/15037752/Catalytic_enantioselective_intermolecular_cycloadditions_of_2_diazo_36_diketoester_derived_carbonyl_ylides_with_alkene_dipolarophiles_ L2 - http://www.pnas.org/cgi/pmidlookup?view=long&pmid=15037752 DB - PRIME DP - Unbound Medicine ER -
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