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Switch of regioselectivity in palladium-catalyzed silaboration of terminal alkynes by ligand-dependent control of reductive elimination.
J Am Chem Soc. 2010 Sep 08; 132(35):12194-6.JA

Abstract

The regioselectivity in the addition of silylboronic esters to terminal alkynes can be switched by the choice of phosphorus ligands on the palladium catalysts. The silaboration proceeds with normal regioselectivity in the presence of (eta(3)-C(3)H(5))Pd(PPh(3))Cl (1.0 mol %) to give 1-boryl-2-silyl-1-alkenes in high yields. In sharp contrast, selective formation of the inverse regioisomers, 2-boryl-1-silyl-1-alkenes, takes place when the reaction is carried out with a palladium catalyst bearing P(t-Bu)(2)(biphenyl-2-yl). A reaction mechanism for the change of regioselectivity that involves reversible insertion/beta-boryl elimination steps is proposed.

Authors+Show Affiliations

Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Katsura, Kyoto 615-8510, Japan. ohmura@sbchem.kyoto-u.ac.jpNo 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

20701274

Citation

Ohmura, Toshimichi, et al. "Switch of Regioselectivity in Palladium-catalyzed Silaboration of Terminal Alkynes By Ligand-dependent Control of Reductive Elimination." Journal of the American Chemical Society, vol. 132, no. 35, 2010, pp. 12194-6.
Ohmura T, Oshima K, Taniguchi H, et al. Switch of regioselectivity in palladium-catalyzed silaboration of terminal alkynes by ligand-dependent control of reductive elimination. J Am Chem Soc. 2010;132(35):12194-6.
Ohmura, T., Oshima, K., Taniguchi, H., & Suginome, M. (2010). Switch of regioselectivity in palladium-catalyzed silaboration of terminal alkynes by ligand-dependent control of reductive elimination. Journal of the American Chemical Society, 132(35), 12194-6. https://doi.org/10.1021/ja105096r
Ohmura T, et al. Switch of Regioselectivity in Palladium-catalyzed Silaboration of Terminal Alkynes By Ligand-dependent Control of Reductive Elimination. J Am Chem Soc. 2010 Sep 8;132(35):12194-6. PubMed PMID: 20701274.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Switch of regioselectivity in palladium-catalyzed silaboration of terminal alkynes by ligand-dependent control of reductive elimination. AU - Ohmura,Toshimichi, AU - Oshima,Kazuyuki, AU - Taniguchi,Hiroki, AU - Suginome,Michinori, PY - 2010/8/13/entrez PY - 2010/8/13/pubmed PY - 2010/12/25/medline SP - 12194 EP - 6 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 132 IS - 35 N2 - The regioselectivity in the addition of silylboronic esters to terminal alkynes can be switched by the choice of phosphorus ligands on the palladium catalysts. The silaboration proceeds with normal regioselectivity in the presence of (eta(3)-C(3)H(5))Pd(PPh(3))Cl (1.0 mol %) to give 1-boryl-2-silyl-1-alkenes in high yields. In sharp contrast, selective formation of the inverse regioisomers, 2-boryl-1-silyl-1-alkenes, takes place when the reaction is carried out with a palladium catalyst bearing P(t-Bu)(2)(biphenyl-2-yl). A reaction mechanism for the change of regioselectivity that involves reversible insertion/beta-boryl elimination steps is proposed. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/20701274/Switch_of_regioselectivity_in_palladium_catalyzed_silaboration_of_terminal_alkynes_by_ligand_dependent_control_of_reductive_elimination_ L2 - https://doi.org/10.1021/ja105096r DB - PRIME DP - Unbound Medicine ER -