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Easy access to isoquinolines and tetrahydroquinolines from ketoximes and alkynes via rhodium-catalyzed C-H bond activation.
J Org Chem. 2009 Dec 18; 74(24):9359-64.JO

Abstract

Described herein is a convenient and highly regioselective synthesis of substituted isoquinoline derivatives from various aromatic ketoximes and alkynes via a one-pot, rhodium-catalyzed C-H bond activation. In addition, tetrahydroquinoline derivatives are formed in good yields from 2-arylidene-1-cyclohexanone oximes possessing an exocyclic double bond and from tetrahydroxanthone oximes. A possible mechanism is proposed that involves chelation-assisted C-H activation via oxidative addition of Rh(I) to an ortho-C-H bond, insertion of the alkyne, reductive elimination, intramolecular electrocyclization, and aromatization. This mechanism is supported by isolation of the ortho-alkenylation products 7p and 7q. Also described herein is an example of an iridium-catalyzed activation of an sp(3) C-H bond.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Parthasarathy K
Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.
Cheng CH
No affiliation info available

MeSH

AlkynesCarbonCatalysisCyclizationHydrogenHydroxyquinolinesIsoquinolinesMagnetic Resonance SpectroscopyOxidation-ReductionOximesRhodiumStereoisomerism

Pub Type(s)

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

Language

eng

PubMed ID

19894732

Citation

Parthasarathy, Kanniyappan, and Chien-Hong Cheng. "Easy Access to Isoquinolines and Tetrahydroquinolines From Ketoximes and Alkynes Via Rhodium-catalyzed C-H Bond Activation." The Journal of Organic Chemistry, vol. 74, no. 24, 2009, pp. 9359-64.
Parthasarathy K, Cheng CH. Easy access to isoquinolines and tetrahydroquinolines from ketoximes and alkynes via rhodium-catalyzed C-H bond activation. J Org Chem. 2009;74(24):9359-64.
Parthasarathy, K., & Cheng, C. H. (2009). Easy access to isoquinolines and tetrahydroquinolines from ketoximes and alkynes via rhodium-catalyzed C-H bond activation. The Journal of Organic Chemistry, 74(24), 9359-64. https://doi.org/10.1021/jo902084j
Parthasarathy K, Cheng CH. Easy Access to Isoquinolines and Tetrahydroquinolines From Ketoximes and Alkynes Via Rhodium-catalyzed C-H Bond Activation. J Org Chem. 2009 Dec 18;74(24):9359-64. PubMed PMID: 19894732.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Easy access to isoquinolines and tetrahydroquinolines from ketoximes and alkynes via rhodium-catalyzed C-H bond activation. AU - Parthasarathy,Kanniyappan, AU - Cheng,Chien-Hong, PY - 2009/11/10/entrez PY - 2009/11/10/pubmed PY - 2010/3/20/medline SP - 9359 EP - 64 JF - The Journal of organic chemistry JO - J Org Chem VL - 74 IS - 24 N2 - Described herein is a convenient and highly regioselective synthesis of substituted isoquinoline derivatives from various aromatic ketoximes and alkynes via a one-pot, rhodium-catalyzed C-H bond activation. In addition, tetrahydroquinoline derivatives are formed in good yields from 2-arylidene-1-cyclohexanone oximes possessing an exocyclic double bond and from tetrahydroxanthone oximes. A possible mechanism is proposed that involves chelation-assisted C-H activation via oxidative addition of Rh(I) to an ortho-C-H bond, insertion of the alkyne, reductive elimination, intramolecular electrocyclization, and aromatization. This mechanism is supported by isolation of the ortho-alkenylation products 7p and 7q. Also described herein is an example of an iridium-catalyzed activation of an sp(3) C-H bond. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/19894732/Easy_access_to_isoquinolines_and_tetrahydroquinolines_from_ketoximes_and_alkynes_via_rhodium_catalyzed_C_H_bond_activation_ L2 - https://doi.org/10.1021/jo902084j DB - PRIME DP - Unbound Medicine ER -