Tags

Type your tag names separated by a space and hit enter

Access to Spirocyclized Oxindoles and Indolenines via Palladium-Catalyzed Cascade Reactions of Propargyl Carbonates with 2-Oxotryptamines and Tryptamines.
J Org Chem. 2015 May 15; 80(10):4928-41.JO

Abstract

Reported here are methods for the direct construction of a range of spirocyclized oxindoles and indolenines in good to excellent yields. Specifically, we report the palladium-catalyzed reactions of oxindoles and indoles, both functioning as bis-nucleophiles, with propargyl carbonates to afford spirocyclic products having an exocyclic double bond on the newly formed ring. The reaction proceeds through a process wherein the first nucleophilic unit on the oxindole or indole reacts with an allenyl-palladium species, formed from oxidative addition of Pd(0) to propargyl carbonates, to generate a π-allyl palladium intermediate that then reacts further with the second nucleophilic component of the oxindole or indole. The cascade process forges two bonds en route to spirocyclized oxindole and indolenine products. The use of chiral phosphines renders the cyclization sequence enantioselective, providing spirocyclic products with modest to good enantioselectivities.

Links

Publisher Full Text (DOI)

Authors+Show Affiliations

Nibbs AE
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.
Montgomery TD
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.
Zhu Y
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.
Rawal VH
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue Chicago, Illinois 60637, United States.

MeSH

CatalysisCyclizationIndolesMolecular StructureOxindolesPalladiumPargylineSpiro CompoundsTryptamines

Pub Type(s)

Journal Article
Research Support, N.I.H., Extramural

Language

eng

PubMed ID

25876139

Citation

Nibbs, Antoinette E., et al. "Access to Spirocyclized Oxindoles and Indolenines Via Palladium-Catalyzed Cascade Reactions of Propargyl Carbonates With 2-Oxotryptamines and Tryptamines." The Journal of Organic Chemistry, vol. 80, no. 10, 2015, pp. 4928-41.
Nibbs AE, Montgomery TD, Zhu Y, et al. Access to Spirocyclized Oxindoles and Indolenines via Palladium-Catalyzed Cascade Reactions of Propargyl Carbonates with 2-Oxotryptamines and Tryptamines. J Org Chem. 2015;80(10):4928-41.
Nibbs, A. E., Montgomery, T. D., Zhu, Y., & Rawal, V. H. (2015). Access to Spirocyclized Oxindoles and Indolenines via Palladium-Catalyzed Cascade Reactions of Propargyl Carbonates with 2-Oxotryptamines and Tryptamines. The Journal of Organic Chemistry, 80(10), 4928-41. https://doi.org/10.1021/acs.joc.5b00277
Nibbs AE, et al. Access to Spirocyclized Oxindoles and Indolenines Via Palladium-Catalyzed Cascade Reactions of Propargyl Carbonates With 2-Oxotryptamines and Tryptamines. J Org Chem. 2015 May 15;80(10):4928-41. PubMed PMID: 25876139.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Access to Spirocyclized Oxindoles and Indolenines via Palladium-Catalyzed Cascade Reactions of Propargyl Carbonates with 2-Oxotryptamines and Tryptamines. AU - Nibbs,Antoinette E, AU - Montgomery,Thomas D, AU - Zhu,Ye, AU - Rawal,Viresh H, Y1 - 2015/04/29/ PY - 2015/4/16/entrez PY - 2015/4/16/pubmed PY - 2015/12/31/medline SP - 4928 EP - 41 JF - The Journal of organic chemistry JO - J Org Chem VL - 80 IS - 10 N2 - Reported here are methods for the direct construction of a range of spirocyclized oxindoles and indolenines in good to excellent yields. Specifically, we report the palladium-catalyzed reactions of oxindoles and indoles, both functioning as bis-nucleophiles, with propargyl carbonates to afford spirocyclic products having an exocyclic double bond on the newly formed ring. The reaction proceeds through a process wherein the first nucleophilic unit on the oxindole or indole reacts with an allenyl-palladium species, formed from oxidative addition of Pd(0) to propargyl carbonates, to generate a π-allyl palladium intermediate that then reacts further with the second nucleophilic component of the oxindole or indole. The cascade process forges two bonds en route to spirocyclized oxindole and indolenine products. The use of chiral phosphines renders the cyclization sequence enantioselective, providing spirocyclic products with modest to good enantioselectivities. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/25876139/Access_to_Spirocyclized_Oxindoles_and_Indolenines_via_Palladium_Catalyzed_Cascade_Reactions_of_Propargyl_Carbonates_with_2_Oxotryptamines_and_Tryptamines_ DB - PRIME DP - Unbound Medicine ER -