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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

Department of Chemistry, University of Bath, Bath BA2 7AY, UK. m.c.willis@bath.ac.ukNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

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://dx.doi.org/10.1021/jo060582o DB - PRIME DP - Unbound Medicine ER -