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Hydrogen-mediated C-C bond formation: catalytic regio- and stereoselective reductive condensation of alpha-keto aldehydes and 1,3-enynes.
J Am Chem Soc. 2004 Apr 14; 126(14):4664-8.JA

Abstract

Hydrogenation of 1,3-enynes in the presence of alpha-keto aldehydes using cationic Rh(I) catalysts enables regio- and stereoselective reductive coupling to the acetylenic terminus of the enyne to afford (E)-2-hydroxy-3,5-dien-1-one products. Reductive condensation of 1-phenyl but-3-en-1-yne 1a with phenyl glyoxal 2a performed under an atmosphere of D(2) provides the product of mono-deuteration, (E)-2-hydroxy-3-deuterio-3,5-dien-1-one deuterio-3a, in 85% yield. Competition experiments involving catalytic hydrogenation of phenyl glyoxal in the presence of equimolar quantities of 1,4-diphenylbutadiene and 1,4-diphenylbut-3-en-1-yne 10a, as well as 1,4-diphenylbut-3-en-1-yne 10a and 1,4-diphenylbutadiyne, are chemoselective for coupling to the more highly unsaturated partner, suggesting a preequilibrium involving precoordination and exchange of the pi-unsaturated pronucleophiles with the catalyst prior to C-C bond formation, as well as a preference for coordination of the most pi-acidic reacting partner, as explained by the Dewar-Chatt-Duncanson model for alkyne coordination.

Authors+Show Affiliations

Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.No affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

15070383

Citation

Jang, Hye-Young, et al. "Hydrogen-mediated C-C Bond Formation: Catalytic Regio- and Stereoselective Reductive Condensation of Alpha-keto Aldehydes and 1,3-enynes." Journal of the American Chemical Society, vol. 126, no. 14, 2004, pp. 4664-8.
Jang HY, Huddleston RR, Krische MJ. Hydrogen-mediated C-C bond formation: catalytic regio- and stereoselective reductive condensation of alpha-keto aldehydes and 1,3-enynes. J Am Chem Soc. 2004;126(14):4664-8.
Jang, H. Y., Huddleston, R. R., & Krische, M. J. (2004). Hydrogen-mediated C-C bond formation: catalytic regio- and stereoselective reductive condensation of alpha-keto aldehydes and 1,3-enynes. Journal of the American Chemical Society, 126(14), 4664-8.
Jang HY, Huddleston RR, Krische MJ. Hydrogen-mediated C-C Bond Formation: Catalytic Regio- and Stereoselective Reductive Condensation of Alpha-keto Aldehydes and 1,3-enynes. J Am Chem Soc. 2004 Apr 14;126(14):4664-8. PubMed PMID: 15070383.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Hydrogen-mediated C-C bond formation: catalytic regio- and stereoselective reductive condensation of alpha-keto aldehydes and 1,3-enynes. AU - Jang,Hye-Young, AU - Huddleston,Ryan R, AU - Krische,Michael J, PY - 2004/4/9/pubmed PY - 2004/6/30/medline PY - 2004/4/9/entrez SP - 4664 EP - 8 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 126 IS - 14 N2 - Hydrogenation of 1,3-enynes in the presence of alpha-keto aldehydes using cationic Rh(I) catalysts enables regio- and stereoselective reductive coupling to the acetylenic terminus of the enyne to afford (E)-2-hydroxy-3,5-dien-1-one products. Reductive condensation of 1-phenyl but-3-en-1-yne 1a with phenyl glyoxal 2a performed under an atmosphere of D(2) provides the product of mono-deuteration, (E)-2-hydroxy-3-deuterio-3,5-dien-1-one deuterio-3a, in 85% yield. Competition experiments involving catalytic hydrogenation of phenyl glyoxal in the presence of equimolar quantities of 1,4-diphenylbutadiene and 1,4-diphenylbut-3-en-1-yne 10a, as well as 1,4-diphenylbut-3-en-1-yne 10a and 1,4-diphenylbutadiyne, are chemoselective for coupling to the more highly unsaturated partner, suggesting a preequilibrium involving precoordination and exchange of the pi-unsaturated pronucleophiles with the catalyst prior to C-C bond formation, as well as a preference for coordination of the most pi-acidic reacting partner, as explained by the Dewar-Chatt-Duncanson model for alkyne coordination. SN - 0002-7863 UR - https://www.unboundmedicine.com/medline/citation/15070383/Hydrogen_mediated_C_C_bond_formation:_catalytic_regio__and_stereoselective_reductive_condensation_of_alpha_keto_aldehydes_and_13_enynes_ L2 - https://doi.org/10.1021/ja0316566 DB - PRIME DP - Unbound Medicine ER -