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Catalytic asymmetric synthesis of chiral propargylic alcohols for the intramolecular Pauson-Khand cycloaddition.
J Org Chem. 2010 Oct 15; 75(20):6941-52.JO

Abstract

Several methods for the catalytic asymmetric alkyne addition to aldehydes are used to prepare the propargylic alcohol-based chiral en-ynes. Protection of the propargylic alcohols with either an acetyl or a methyl group allows the resulting en-ynes to undergo the intramolecular Pauson-Khand reaction to form the corresponding optically active 5,5- and 5,6-fused bicyclic products with high diastereoselectivity and high enantiomeric purity. In the major product, the propargylic substituent and the bridgehead hydrogen are cis with respect to each other on the fused bicyclic rings. The enantiomeric purity of the propargylic alcohols generated from the asymmetric alkyne addition is maintained in the cycloaddition products. The allylic ethers of the chiral propargylic alcohols are prepared which can also undergo the highly diastereoselective Pauson-Khand cycloaddition with retention of the high enantiomeric purity. This study has shown that the size of the substituents at the propargylic position as well as on the alkyne is important for the diastereoselectivity with the greater bulkiness of the substituents giving higher diastereoselectivity.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Turlington M
Department of Chemistry, University of Virginia, Charlottesville, Virginia 22904, USA.
Yue Y
No affiliation info available
Yu XQ
No affiliation info available
Pu L
No affiliation info available

MeSH

AlkynesCatalysisCyclizationMolecular StructureOrganometallic CompoundsPropanolsStereoisomerismZinc

Pub Type(s)

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

Language

eng

PubMed ID

20843029

Citation

Turlington, Mark, et al. "Catalytic Asymmetric Synthesis of Chiral Propargylic Alcohols for the Intramolecular Pauson-Khand Cycloaddition." The Journal of Organic Chemistry, vol. 75, no. 20, 2010, pp. 6941-52.
Turlington M, Yue Y, Yu XQ, et al. Catalytic asymmetric synthesis of chiral propargylic alcohols for the intramolecular Pauson-Khand cycloaddition. J Org Chem. 2010;75(20):6941-52.
Turlington, M., Yue, Y., Yu, X. Q., & Pu, L. (2010). Catalytic asymmetric synthesis of chiral propargylic alcohols for the intramolecular Pauson-Khand cycloaddition. The Journal of Organic Chemistry, 75(20), 6941-52. https://doi.org/10.1021/jo101545v
Turlington M, et al. Catalytic Asymmetric Synthesis of Chiral Propargylic Alcohols for the Intramolecular Pauson-Khand Cycloaddition. J Org Chem. 2010 Oct 15;75(20):6941-52. PubMed PMID: 20843029.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Catalytic asymmetric synthesis of chiral propargylic alcohols for the intramolecular Pauson-Khand cycloaddition. AU - Turlington,Mark, AU - Yue,Yang, AU - Yu,Xiao-Qi, AU - Pu,Lin, PY - 2010/9/17/entrez PY - 2010/9/17/pubmed PY - 2011/1/28/medline SP - 6941 EP - 52 JF - The Journal of organic chemistry JO - J Org Chem VL - 75 IS - 20 N2 - Several methods for the catalytic asymmetric alkyne addition to aldehydes are used to prepare the propargylic alcohol-based chiral en-ynes. Protection of the propargylic alcohols with either an acetyl or a methyl group allows the resulting en-ynes to undergo the intramolecular Pauson-Khand reaction to form the corresponding optically active 5,5- and 5,6-fused bicyclic products with high diastereoselectivity and high enantiomeric purity. In the major product, the propargylic substituent and the bridgehead hydrogen are cis with respect to each other on the fused bicyclic rings. The enantiomeric purity of the propargylic alcohols generated from the asymmetric alkyne addition is maintained in the cycloaddition products. The allylic ethers of the chiral propargylic alcohols are prepared which can also undergo the highly diastereoselective Pauson-Khand cycloaddition with retention of the high enantiomeric purity. This study has shown that the size of the substituents at the propargylic position as well as on the alkyne is important for the diastereoselectivity with the greater bulkiness of the substituents giving higher diastereoselectivity. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/20843029/Catalytic_asymmetric_synthesis_of_chiral_propargylic_alcohols_for_the_intramolecular_Pauson_Khand_cycloaddition_ L2 - https://doi.org/10.1021/jo101545v DB - PRIME DP - Unbound Medicine ER -