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Lanthanum Catalyzed Hydrophosphination and Hydrophosphinylation

Basiouny, Miriam M.I.
http://rave.ohiolink.edu/etdc/view?acc_num=toledo1525441044040006

Abstract Details

2018, Doctor of Philosophy, University of Toledo, Chemistry.
Phosphines and phosphine oxides have been indispensable tools in different areas of chemistry including organometallics, pharmaceuticals, and agrochemicals. With the increasing need of specialized phosphines and phosphine oxides, chemists turned to catalytic hydrophosphination (the addition of an H-P bond across an unsaturated system) and hydrophosphinylation (the addition of an H-P(O) bond across an unsaturated system). A lanthanum (III) catalyst supported by a-metalated N,N-dimethylbenzylamine ligands (La(Dmba)3) was used to induce the first example of direct double hydrophosphinylation of unactivated nitriles, yielding different regioisomeric products depending on the nature of the nitrile. Primary alkyl nitriles undergo 1,1-addition to give products with a new P-C-P linkage and a primary amine. Secondary and aryl nitriles undergo 1,2-addition to yield a new P-C-N-P linkage under the same conditions. Further investigation into the catalytic cycle showed that all nitriles first undergo 1,1-addition and then undergo isomerization to the final unsymmetric product. La(Dmba)3 was also the first catalyst to induce both hydrophosphination and hydrophosphinylation of alkynes under mild conditions. This too showed interesting selectivity. In the case of hydrophosphination, the catalyst induced mono-addition with high regiospecificity, yielding only the anti-Markovnikov product. The stereoselectivity of the final products can be controlled based on the reaction conditions. Undertaking the catalysis with excess phosphine yielded the E-isomer as the major product; however, using excess alkyne, the Z-isomer was isolated as the major product. A brief investigation into the catalytic cycle suggests that a dimeric form of lanthanum phosphide active catalyst forms the Z-isomers as kinetic products that then undergo isomerization to yield the final E-isomers. In the case of hydrophosphinylation, the chemoselectivity depended on the nature of alkyne. Terminal alkynes only showed double addition products while single and double addition products were both successfully isolated in the case of internal alkynes. This reaction also showed high chemo-and regioselectivity. The lanthanum-based catalyst was shown to be very effective in inducing unusual hydrophosphination and hydrophosphinylation products with high control of selectivity.
Joseph A.R. Schmidt (Committee Chair)
Mark R. Mason (Committee Member)
Steven J. Sucheck (Committee Member)
Constance A. Schall (Committee Member)
Chemistry

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Citations

  • Basiouny, M. M.I. (2018). Lanthanum Catalyzed Hydrophosphination and Hydrophosphinylation [Doctoral dissertation, University of Toledo]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1525441044040006

    APA Style (7th edition)

  • Basiouny, Miriam. Lanthanum Catalyzed Hydrophosphination and Hydrophosphinylation. 2018. University of Toledo, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=toledo1525441044040006.

    MLA Style (8th edition)

  • Basiouny, Miriam. "Lanthanum Catalyzed Hydrophosphination and Hydrophosphinylation." Doctoral dissertation, University of Toledo, 2018. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1525441044040006

    Chicago Manual of Style (17th edition)

toledo1525441044040006
416
© , some rights reserved.Creative Commons License Lanthanum Catalyzed Hydrophosphination and Hydrophosphinylation by Miriam M.I. Basiouny is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License. Based on a work at etd.ohiolink.edu.
This open access ETD is published by University of Toledo and OhioLINK.