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Dicobaltoctacarbonyl-mediated synthesis of tricyclic 5,6-diydropyran-2-one derivatives via tandem cycloaddition reaction between cis-epoxyalkynes, a tethered olefin, and carbon monoxide.
J Org Chem. 2007 Jan 19; 72(2):567-73.JO

Abstract

Cobalt carbonyl complex Co2(CO)8 implemented an intramolecular carbonylation of cis-epoxyalkynes to generate Co2(CO)6-stabilized gamma-lactonyl allene species. For 1,1,2-trisubstituted epoxyalkynes, this Co2(CO)6-allene species reacted with a tethered olefin to give [2+2]-cycloadducts, and with CO and a tethered olefin to produce [2+2+1]-cycloadducts. These resulting cycloadducts have a 5,6-diydropyran-2-one core fused with a cyclobutane and a cyclopentanone ring, respectively. For 1,2-disubstituted cis-epoxyalkyne and 1,1,2-trisubstituted cis-epoxyalkynes bearing a heteroatom constituent, cyclization of the corresponding epoxyalkyne with a tethered alkene is invariably accompanied by incorporation of CO to produce a [2+2+1]-cycloadduct, even in the absence of CO. We have prepared various 1,1,2-trisubstituted and 1,2-disubstituted cis-epoxyalkynes to generalize such cycloaddition pathways. Attempt to use an organic promoter to perform these tandem cycloadditions was unsuccessful because of a competing Pauson-Khand reaction. Cyclization of a 1,2-disubstituted epoxyalkyne with a tethered diene was achieved successfully in one case, but the yield was low (25%).

Authors+Show Affiliations

Odedra A
Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan, ROC.
Lush SF
No affiliation info available
Liu RS
No affiliation info available

MeSH

AlkenesAlkynesCarbon MonoxideCobaltCyclizationEpoxy CompoundsMolecular ConformationOrganometallic CompoundsPyransStereoisomerism

Pub Type(s)

Journal Article

Language

eng

PubMed ID

17221975

Citation

Odedra, Arjan, et al. "Dicobaltoctacarbonyl-mediated Synthesis of Tricyclic 5,6-diydropyran-2-one Derivatives Via Tandem Cycloaddition Reaction Between Cis-epoxyalkynes, a Tethered Olefin, and Carbon Monoxide." The Journal of Organic Chemistry, vol. 72, no. 2, 2007, pp. 567-73.
Odedra A, Lush SF, Liu RS. Dicobaltoctacarbonyl-mediated synthesis of tricyclic 5,6-diydropyran-2-one derivatives via tandem cycloaddition reaction between cis-epoxyalkynes, a tethered olefin, and carbon monoxide. J Org Chem. 2007;72(2):567-73.
Odedra, A., Lush, S. F., & Liu, R. S. (2007). Dicobaltoctacarbonyl-mediated synthesis of tricyclic 5,6-diydropyran-2-one derivatives via tandem cycloaddition reaction between cis-epoxyalkynes, a tethered olefin, and carbon monoxide. The Journal of Organic Chemistry, 72(2), 567-73.
Odedra A, Lush SF, Liu RS. Dicobaltoctacarbonyl-mediated Synthesis of Tricyclic 5,6-diydropyran-2-one Derivatives Via Tandem Cycloaddition Reaction Between Cis-epoxyalkynes, a Tethered Olefin, and Carbon Monoxide. J Org Chem. 2007 Jan 19;72(2):567-73. PubMed PMID: 17221975.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Dicobaltoctacarbonyl-mediated synthesis of tricyclic 5,6-diydropyran-2-one derivatives via tandem cycloaddition reaction between cis-epoxyalkynes, a tethered olefin, and carbon monoxide. AU - Odedra,Arjan, AU - Lush,Shie-Fu, AU - Liu,Rai-Shung, PY - 2007/1/16/pubmed PY - 2007/3/21/medline PY - 2007/1/16/entrez SP - 567 EP - 73 JF - The Journal of organic chemistry JO - J Org Chem VL - 72 IS - 2 N2 - Cobalt carbonyl complex Co2(CO)8 implemented an intramolecular carbonylation of cis-epoxyalkynes to generate Co2(CO)6-stabilized gamma-lactonyl allene species. For 1,1,2-trisubstituted epoxyalkynes, this Co2(CO)6-allene species reacted with a tethered olefin to give [2+2]-cycloadducts, and with CO and a tethered olefin to produce [2+2+1]-cycloadducts. These resulting cycloadducts have a 5,6-diydropyran-2-one core fused with a cyclobutane and a cyclopentanone ring, respectively. For 1,2-disubstituted cis-epoxyalkyne and 1,1,2-trisubstituted cis-epoxyalkynes bearing a heteroatom constituent, cyclization of the corresponding epoxyalkyne with a tethered alkene is invariably accompanied by incorporation of CO to produce a [2+2+1]-cycloadduct, even in the absence of CO. We have prepared various 1,1,2-trisubstituted and 1,2-disubstituted cis-epoxyalkynes to generalize such cycloaddition pathways. Attempt to use an organic promoter to perform these tandem cycloadditions was unsuccessful because of a competing Pauson-Khand reaction. Cyclization of a 1,2-disubstituted epoxyalkyne with a tethered diene was achieved successfully in one case, but the yield was low (25%). SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/17221975/Dicobaltoctacarbonyl_mediated_synthesis_of_tricyclic_56_diydropyran_2_one_derivatives_via_tandem_cycloaddition_reaction_between_cis_epoxyalkynes_a_tethered_olefin_and_carbon_monoxide_ L2 - https://doi.org/10.1021/jo0620617 DB - PRIME DP - Unbound Medicine ER -