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Cationic Cobalt(I)-Mediated Heterodimerizations: From Mechanistic Insights to Reaction Discovery

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2017, Doctor of Philosophy, Ohio State University, Chemistry.
The use of abundantly available feedstock such as ethylene, carbon monoxide, hydrogen cyanide, alkyl acrylates, in fine chemical synthesis is a major challenge in organic synthesis, and developing asymmetric versions of reactions which makes use of these feedstock chemicals is an even bigger challenge. The detailed mechanism of a recently discovered cobalt-mediated hydrovinylation of prochiral dienes has been studied. The role of trimethyl aluminum employed as an activator of the cobalt(II)-dihalide complex employed for the cobalt-mediate hydrovinylation has been determined to be: reduction of Co(II)-complex to Co(I)-complex and generation of cationic-Co(I) species as active catalyst. Well defined Co(I)-complexes were synthesized and characterized via NMR spectroscopy and crystallography. Treatment of these Co(I) complexes with various activators such as NaBARF, ZnCl2, B(C6F5)3, generates cationic Co(I) which mediates the reaction. This new protocol for hydrovinylation was successfully employed for a broadly applicable asymmetric heterodimerization of acrylates and 1,3-dienes. The reaction tolerates other functional groups such as olefins, alcohols, alkyl halides, trialkylsiloxy-, and even sensitive silyl enol ethers.
T.V. RajanBabu (Advisor)
Jon Parquette (Committee Member)
Jovica Badjic (Committee Member)
458 p.

Recommended Citations

Citations

  • Jing, S. M. (2017). Cationic Cobalt(I)-Mediated Heterodimerizations: From Mechanistic Insights to Reaction Discovery [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1503302900762289

    APA Style (7th edition)

  • Jing, Stanley . Cationic Cobalt(I)-Mediated Heterodimerizations: From Mechanistic Insights to Reaction Discovery. 2017. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1503302900762289.

    MLA Style (8th edition)

  • Jing, Stanley . "Cationic Cobalt(I)-Mediated Heterodimerizations: From Mechanistic Insights to Reaction Discovery." Doctoral dissertation, Ohio State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=osu1503302900762289

    Chicago Manual of Style (17th edition)