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Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates.
J Org Chem. 2006 Jul 07; 71(14):5291-7.JO

Abstract

The use of beta-S-substituted aldehydes in rhodium-catalyzed intermolecular hydroacylation reactions is reported. Aldehydes substituted with either sulfide or thioacetal groups undergo efficient hydroacylation with a variety of electron-poor alkenes, such as enoates, in Stetter-like processes and with both electron-poor and neutral alkynes. In general, the reactions with electron-poor alkenes demonstrate good selectivity for the linear regioisomer, and the reactions with alkynes provide enone products with excellent selectivity for the E-isomers. The scope of the process was shown to be broad, tolerating a variety of substitution patterns and functional groups on both reaction components. A novel CN-directing effect was shown to be responsible for reversing the regioselectivity in a number of alkyne hydroacylation reactions. Catalyst loadings as low as 0.1 mol % were achievable.

Authors+Show Affiliations

Willis MC
Department of Chemistry, University of Bath, Bath BA2 7AY, UK. m.c.willis@bath.ac.uk
Randell-Sly HE
No affiliation info available
Woodward RL
No affiliation info available
McNally SJ
No affiliation info available
Currie GS
No affiliation info available

MeSH

AldehydesAlkenesAlkynesCatalysisKetonesMolecular StructureRhodiumStereoisomerism

Pub Type(s)

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

Language

eng

PubMed ID

16808518

Citation

Willis, Michael C., et al. "Rhodium-catalyzed Intermolecular Chelation Controlled Alkene and Alkyne Hydroacylation: Synthetic Scope of beta-S-substituted Aldehyde Substrates." The Journal of Organic Chemistry, vol. 71, no. 14, 2006, pp. 5291-7.
Willis MC, Randell-Sly HE, Woodward RL, et al. Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. J Org Chem. 2006;71(14):5291-7.
Willis, M. C., Randell-Sly, H. E., Woodward, R. L., McNally, S. J., & Currie, G. S. (2006). Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. The Journal of Organic Chemistry, 71(14), 5291-7.
Willis MC, et al. Rhodium-catalyzed Intermolecular Chelation Controlled Alkene and Alkyne Hydroacylation: Synthetic Scope of beta-S-substituted Aldehyde Substrates. J Org Chem. 2006 Jul 7;71(14):5291-7. PubMed PMID: 16808518.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Rhodium-catalyzed intermolecular chelation controlled alkene and alkyne hydroacylation: synthetic scope of beta-S-substituted aldehyde substrates. AU - Willis,Michael C, AU - Randell-Sly,Helen E, AU - Woodward,Robert L, AU - McNally,Steven J, AU - Currie,Gordon S, PY - 2006/7/1/pubmed PY - 2007/6/28/medline PY - 2006/7/1/entrez SP - 5291 EP - 7 JF - The Journal of organic chemistry JO - J Org Chem VL - 71 IS - 14 N2 - The use of beta-S-substituted aldehydes in rhodium-catalyzed intermolecular hydroacylation reactions is reported. Aldehydes substituted with either sulfide or thioacetal groups undergo efficient hydroacylation with a variety of electron-poor alkenes, such as enoates, in Stetter-like processes and with both electron-poor and neutral alkynes. In general, the reactions with electron-poor alkenes demonstrate good selectivity for the linear regioisomer, and the reactions with alkynes provide enone products with excellent selectivity for the E-isomers. The scope of the process was shown to be broad, tolerating a variety of substitution patterns and functional groups on both reaction components. A novel CN-directing effect was shown to be responsible for reversing the regioselectivity in a number of alkyne hydroacylation reactions. Catalyst loadings as low as 0.1 mol % were achievable. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/16808518/Rhodium_catalyzed_intermolecular_chelation_controlled_alkene_and_alkyne_hydroacylation:_synthetic_scope_of_beta_S_substituted_aldehyde_substrates_ L2 - https://doi.org/10.1021/jo060582o DB - PRIME DP - Unbound Medicine ER -