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New general method for regio- and stereoselective allylic substitution with aryl and alkenyl coppers derived from Grignard reagents.
J Org Chem. 2009 Mar 06; 74(5):1939-51.JO

Abstract

Allylic substitution with sp(2)-carbon reagents (aryl and alkenyl anions) was realized by using allylic picolinates and copper reagents derived from RMgBr and CuBr x Me(2)S to afford anti S(N)2' products regio- and stereoselectively. Steric and electronic factors in the reagents and the size of the methylene substituents around the allylic moiety marginally affected the selectivity. The reaction system was compatible with alkyl reagents as well. Furthermore, the substitution was applied to construction of a quaternary center and synthesis of (-)-sesquichamaenol. Electron-withdrawing nature of the pyridyl group and chelation of the C(=O)-C(5)H(4)N to MgBr(2) generated in situ were found to be responsible for the high efficiency of the substitution.

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Publisher Full Text (DOI)

Authors+Show Affiliations

Kiyotsuka Y
Department of Biomolecular Engineering, Tokyo Institute of Technology, Box B52, Nagatsuta-cho 4259, Midori-ku, Yokohama 226-8501, Japan.
Katayama Y
No affiliation info available
Acharya HP
No affiliation info available
Hyodo T
No affiliation info available
Kobayashi Y
No affiliation info available

MeSH

AlkenesAllyl CompoundsCopperMolecular StructureOrganometallic CompoundsStereoisomerism

Pub Type(s)

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

Language

eng

PubMed ID

19199795

Citation

Kiyotsuka, Yohei, et al. "New General Method for Regio- and Stereoselective Allylic Substitution With Aryl and Alkenyl Coppers Derived From Grignard Reagents." The Journal of Organic Chemistry, vol. 74, no. 5, 2009, pp. 1939-51.
Kiyotsuka Y, Katayama Y, Acharya HP, et al. New general method for regio- and stereoselective allylic substitution with aryl and alkenyl coppers derived from Grignard reagents. J Org Chem. 2009;74(5):1939-51.
Kiyotsuka, Y., Katayama, Y., Acharya, H. P., Hyodo, T., & Kobayashi, Y. (2009). New general method for regio- and stereoselective allylic substitution with aryl and alkenyl coppers derived from Grignard reagents. The Journal of Organic Chemistry, 74(5), 1939-51. https://doi.org/10.1021/jo802426g
Kiyotsuka Y, et al. New General Method for Regio- and Stereoselective Allylic Substitution With Aryl and Alkenyl Coppers Derived From Grignard Reagents. J Org Chem. 2009 Mar 6;74(5):1939-51. PubMed PMID: 19199795.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - New general method for regio- and stereoselective allylic substitution with aryl and alkenyl coppers derived from Grignard reagents. AU - Kiyotsuka,Yohei, AU - Katayama,Yuji, AU - Acharya,Hukum P, AU - Hyodo,Tomonori, AU - Kobayashi,Yuichi, PY - 2009/2/10/entrez PY - 2009/2/10/pubmed PY - 2010/8/31/medline SP - 1939 EP - 51 JF - The Journal of organic chemistry JO - J Org Chem VL - 74 IS - 5 N2 - Allylic substitution with sp(2)-carbon reagents (aryl and alkenyl anions) was realized by using allylic picolinates and copper reagents derived from RMgBr and CuBr x Me(2)S to afford anti S(N)2' products regio- and stereoselectively. Steric and electronic factors in the reagents and the size of the methylene substituents around the allylic moiety marginally affected the selectivity. The reaction system was compatible with alkyl reagents as well. Furthermore, the substitution was applied to construction of a quaternary center and synthesis of (-)-sesquichamaenol. Electron-withdrawing nature of the pyridyl group and chelation of the C(=O)-C(5)H(4)N to MgBr(2) generated in situ were found to be responsible for the high efficiency of the substitution. SN - 1520-6904 UR - https://www.unboundmedicine.com/medline/citation/19199795/New_general_method_for_regio__and_stereoselective_allylic_substitution_with_aryl_and_alkenyl_coppers_derived_from_Grignard_reagents_ L2 - https://doi.org/10.1021/jo802426g DB - PRIME DP - Unbound Medicine ER -