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Direct, facile aldehyde and ketone alpha-selenenylation reactions promoted by L-prolinamide and pyrrolidine sulfonamide organocatalysts.
J Org Chem. 2005 Jul 08; 70(14):5678-87.JO

Abstract

[reaction: see text] A new catalytic method for direct alpha-selenenylation reactions of aldehydes and ketones has been developed. The results of exploratory studies have demonstrated that L-prolinamide is an effective catalyst for alpha-selenenylation reactions of aldehydes, whereas pyrrolidine trifluoromethanesulfonamide efficiently promotes reactions of ketones. Under optimized reaction conditions, using N-(phenylseleno)phthalimide as the selenenylation reagent in CH2Cl2 in the presence of L-prolinamide (2 mol %) or pyrrolidine trifluoromethanesulfonamide (10 mol %), a variety of aldehydes and ketones undergo this process to generate alpha-selenenylation products in high yields. Mechanistic insight into the L-proline and L-prolinamide catalyzed alpha-selenenylation reactions of aldehydes with N-(phenylseleno)phthalimide has come from theoretical studies employing ab initio methods and density functional theory. The results reveal that (1) the rate-limiting step of the process involves attack of the enamine intermediate at selenium in N-(phenylseleno)phthalimide and (2) the energy of the transition state for the reaction catalyzed by prolinamide is lower than that promoted by proline. This result is consistent with experimental observations. The role of hydrogen bond interactions in stabilizing the transition states for this process is also discussed.

Authors+Show Affiliations

Wang J
Department of Chemistry, University of New Mexico, Albuquerque, New Mexico 87131, USA.
Li H
No affiliation info available
Mei Y
No affiliation info available
Lou B
No affiliation info available
Xu D
No affiliation info available
Xie D
No affiliation info available
Guo H
No affiliation info available
Wang W
No affiliation info available

MeSH

AldehydesCatalysisKetonesModels, ChemicalProlinePyrrolidinesSeleniumStereoisomerismSulfonamides

Pub Type(s)

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

Language

eng

PubMed ID

15989353

Citation

Wang, Jian, et al. "Direct, Facile Aldehyde and Ketone Alpha-selenenylation Reactions Promoted By L-prolinamide and Pyrrolidine Sulfonamide Organocatalysts." The Journal of Organic Chemistry, vol. 70, no. 14, 2005, pp. 5678-87.
Wang J, Li H, Mei Y, et al. Direct, facile aldehyde and ketone alpha-selenenylation reactions promoted by L-prolinamide and pyrrolidine sulfonamide organocatalysts. J Org Chem. 2005;70(14):5678-87.
Wang, J., Li, H., Mei, Y., Lou, B., Xu, D., Xie, D., Guo, H., & Wang, W. (2005). Direct, facile aldehyde and ketone alpha-selenenylation reactions promoted by L-prolinamide and pyrrolidine sulfonamide organocatalysts. The Journal of Organic Chemistry, 70(14), 5678-87.
Wang J, et al. Direct, Facile Aldehyde and Ketone Alpha-selenenylation Reactions Promoted By L-prolinamide and Pyrrolidine Sulfonamide Organocatalysts. J Org Chem. 2005 Jul 8;70(14):5678-87. PubMed PMID: 15989353.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Direct, facile aldehyde and ketone alpha-selenenylation reactions promoted by L-prolinamide and pyrrolidine sulfonamide organocatalysts. AU - Wang,Jian, AU - Li,Hao, AU - Mei,Yujiang, AU - Lou,Bihshow, AU - Xu,Dingguo, AU - Xie,Daiqian, AU - Guo,Hua, AU - Wang,Wei, PY - 2005/7/2/pubmed PY - 2005/9/1/medline PY - 2005/7/2/entrez SP - 5678 EP - 87 JF - The Journal of organic chemistry JO - J Org Chem VL - 70 IS - 14 N2 - [reaction: see text] A new catalytic method for direct alpha-selenenylation reactions of aldehydes and ketones has been developed. The results of exploratory studies have demonstrated that L-prolinamide is an effective catalyst for alpha-selenenylation reactions of aldehydes, whereas pyrrolidine trifluoromethanesulfonamide efficiently promotes reactions of ketones. Under optimized reaction conditions, using N-(phenylseleno)phthalimide as the selenenylation reagent in CH2Cl2 in the presence of L-prolinamide (2 mol %) or pyrrolidine trifluoromethanesulfonamide (10 mol %), a variety of aldehydes and ketones undergo this process to generate alpha-selenenylation products in high yields. Mechanistic insight into the L-proline and L-prolinamide catalyzed alpha-selenenylation reactions of aldehydes with N-(phenylseleno)phthalimide has come from theoretical studies employing ab initio methods and density functional theory. The results reveal that (1) the rate-limiting step of the process involves attack of the enamine intermediate at selenium in N-(phenylseleno)phthalimide and (2) the energy of the transition state for the reaction catalyzed by prolinamide is lower than that promoted by proline. This result is consistent with experimental observations. The role of hydrogen bond interactions in stabilizing the transition states for this process is also discussed. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/15989353/Direct_facile_aldehyde_and_ketone_alpha_selenenylation_reactions_promoted_by_L_prolinamide_and_pyrrolidine_sulfonamide_organocatalysts_ DB - PRIME DP - Unbound Medicine ER -