Palladium-catalyzed oxidative arylhalogenation of alkenes: synthetic scope and mechanistic insights. 2010

Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
University of Michigan, Department of Chemistry, 930 North University Avenue, Ann Arbor, Michigan 48109, USA.

This article describes the development of a Pd-catalyzed reaction for the arylhalogenation (halogen = Cl or Br) of diverse alpha-olefins by oxidatively intercepting Mizoroki-Heck intermediates. These transformations afford synthetically useful 1,2- and 1,1-arylhalogenated products in good yields with good to excellent selectivities that can be modulated by changing the nature of the halogenating reagent and/or the reaction conditions. The selectivity of these reactions can be rationally tuned by (i) controlling the relative rates of oxidative functionalization versus beta-hydride elimination from equilibrating Pd(II)-alkyl species and (ii) stabilization of organometallic Pd(II) intermediates through the formation of pi-benzyl adducts. These arylhalogenations exhibit modest to excellent levels of stereoselectivity, and the key carbon-halogen bond-forming step proceeds with predominant retention of stereochemistry at carbon.

UI MeSH Term Description Entries
D009281 Naphthalenes Two-ring crystalline hydrocarbons isolated from coal tar. They are used as intermediates in chemical synthesis, as insect repellents, fungicides, lubricants, preservatives, and, formerly, as topical antiseptics.
D010084 Oxidation-Reduction A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471). Redox,Oxidation Reduction
D010165 Palladium A chemical element having an atomic weight of 106.4, atomic number of 46, and the symbol Pd. It is a white, ductile metal resembling platinum, and following it in abundance and importance of applications. It is used in dentistry in the form of gold, silver, and copper alloys.
D002384 Catalysis The facilitation of a chemical reaction by material (catalyst) that is not consumed by the reaction. Catalyses
D000475 Alkenes Unsaturated hydrocarbons of the type Cn-H2n, indicated by the suffix -ene. (Grant & Hackh's Chemical Dictionary, 5th ed, p408) Alkene,Olefin,Olefins,Pentene,Pentenes
D012997 Solvents Liquids that dissolve other substances (solutes), generally solids, without any change in chemical composition, as, water containing sugar. (Grant & Hackh's Chemical Dictionary, 5th ed) Solvent
D013237 Stereoisomerism The phenomenon whereby compounds whose molecules have the same number and kind of atoms and the same atomic arrangement, but differ in their spatial relationships. (From McGraw-Hill Dictionary of Scientific and Technical Terms, 5th ed) Molecular Stereochemistry,Stereoisomers,Stereochemistry, Molecular,Stereoisomer
D013379 Substrate Specificity A characteristic feature of enzyme activity in relation to the kind of substrate on which the enzyme or catalytic molecule reacts. Specificities, Substrate,Specificity, Substrate,Substrate Specificities
D054879 Halogenation Covalent attachment of HALOGENS to other compounds. Bromination,Chlorination,Fluorination,Iodination,Iodation
D020058 Styrene A colorless, toxic liquid with a strong aromatic odor. It is used to make rubbers, polymers and copolymers, and polystyrene plastics. Styrene Monomer,Styrol,Vinylbenzene,Monomer, Styrene

Related Publications

Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
September 2019, Journal of the American Chemical Society,
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
November 2012, Chemistry (Weinheim an der Bergstrasse, Germany),
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
June 2019, Journal of the American Chemical Society,
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
January 2024, Chemistry, an Asian journal,
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
May 2023, The Journal of organic chemistry,
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
July 2014, ACS catalysis,
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
August 2011, Chemistry, an Asian journal,
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
March 2005, Journal of the American Chemical Society,
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
October 2013, Chemical communications (Cambridge, England),
Dipannita Kalyani, and Andrew D Satterfield, and Melanie S Sanford
May 2005, Journal of the American Chemical Society,
Copied contents to your clipboard!