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Palladium-catalyzed gamma-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids.
J Am Chem Soc. 2010 Jan 20; 132(2):879-89.JA

Abstract

Reactions between acyclic (E)-allylic acetates and arylboronic acids in the presence of a palladium catalyst prepared from Pd(OAc)(2), phenanthroline (or bipyridine), and AgSbF(6) (1:1.2:1) proceeded with excellent gamma-selectivity to afford allyl-aryl coupling products with E-configuration. The reactions of alpha-chiral allylic acetates took place with excellent alpha-to-gamma chirality transfer with syn stereochemistry to give allylated arenes with a stereogenic center at the benzylic position. The reaction tolerated a broad range of functional groups in both the allylic acetates and the arylboronic acids. Furthermore, gamma-arylation of cinnamyl alcohol derivatives afforded gem-diarylalkane derivatives containing an unconjugated alkenic substituent. The synthetic utility of this method was demonstrated by its utilization in an efficient synthesis of (+)-sertraline, an antidepressant agent. The observed gamma-regioselectivity and E-1,3-syn stereochemistry were rationalized based on a Pd(II) mechanism involving transmetalation between a cationic mono(acyloxo)palladium(II) complex and arylboronic acid, and directed carbopalladation followed by syn-beta-acyloxy elimination. The results of stoichiometric reactions of palladium complexes related to possible intermediates were fully consistent with the proposed mechanism.

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Authors+Show Affiliations

Ohmiya H
Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Makida Y
No affiliation info available
Li D
No affiliation info available
Tanabe M
No affiliation info available
Sawamura M
No affiliation info available

MeSH

AlkanesBoronic AcidsCatalysisMolecular StructureOrganometallic CompoundsPalladiumPropanolsSertralineStereoisomerism

Pub Type(s)

Journal Article

Language

eng

PubMed ID

20030361

Citation

Ohmiya, Hirohisa, et al. "Palladium-catalyzed Gamma-selective and Stereospecific Allyl-aryl Coupling Between Acyclic Allylic Esters and Arylboronic Acids." Journal of the American Chemical Society, vol. 132, no. 2, 2010, pp. 879-89.
Ohmiya H, Makida Y, Li D, et al. Palladium-catalyzed gamma-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids. J Am Chem Soc. 2010;132(2):879-89.
Ohmiya, H., Makida, Y., Li, D., Tanabe, M., & Sawamura, M. (2010). Palladium-catalyzed gamma-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids. Journal of the American Chemical Society, 132(2), 879-89. https://doi.org/10.1021/ja9092264
Ohmiya H, et al. Palladium-catalyzed Gamma-selective and Stereospecific Allyl-aryl Coupling Between Acyclic Allylic Esters and Arylboronic Acids. J Am Chem Soc. 2010 Jan 20;132(2):879-89. PubMed PMID: 20030361.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Palladium-catalyzed gamma-selective and stereospecific allyl-aryl coupling between acyclic allylic esters and arylboronic acids. AU - Ohmiya,Hirohisa, AU - Makida,Yusuke, AU - Li,Dong, AU - Tanabe,Masahito, AU - Sawamura,Masaya, PY - 2009/12/25/entrez PY - 2009/12/25/pubmed PY - 2010/3/27/medline SP - 879 EP - 89 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 132 IS - 2 N2 - Reactions between acyclic (E)-allylic acetates and arylboronic acids in the presence of a palladium catalyst prepared from Pd(OAc)(2), phenanthroline (or bipyridine), and AgSbF(6) (1:1.2:1) proceeded with excellent gamma-selectivity to afford allyl-aryl coupling products with E-configuration. The reactions of alpha-chiral allylic acetates took place with excellent alpha-to-gamma chirality transfer with syn stereochemistry to give allylated arenes with a stereogenic center at the benzylic position. The reaction tolerated a broad range of functional groups in both the allylic acetates and the arylboronic acids. Furthermore, gamma-arylation of cinnamyl alcohol derivatives afforded gem-diarylalkane derivatives containing an unconjugated alkenic substituent. The synthetic utility of this method was demonstrated by its utilization in an efficient synthesis of (+)-sertraline, an antidepressant agent. The observed gamma-regioselectivity and E-1,3-syn stereochemistry were rationalized based on a Pd(II) mechanism involving transmetalation between a cationic mono(acyloxo)palladium(II) complex and arylboronic acid, and directed carbopalladation followed by syn-beta-acyloxy elimination. The results of stoichiometric reactions of palladium complexes related to possible intermediates were fully consistent with the proposed mechanism. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/20030361/Palladium_catalyzed_gamma_selective_and_stereospecific_allyl_aryl_coupling_between_acyclic_allylic_esters_and_arylboronic_acids_ DB - PRIME DP - Unbound Medicine ER -