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Breaking New Ground with the Suzuki-Miyaura Reaction: Stereoselective Cross-Couplings of 1,1-Diboronyl Alkanes Open Access


Other title
stereoselective couplings
Type of item
Degree grantor
University of Alberta
Author or creator
Sun, Ho-Yan
Supervisor and department
Hall, Dennis G. (Chemistry)
Examining committee member and department
Lundgren, Rylan (Chemistry)
Clive, Derrick (Chemistry)
Jarvo, Elizabeth (Chemistry)
Gibbs-Davis, Julianne (Chemistry)
Department of Chemistry

Date accepted
Graduation date
Doctor of Philosophy
Degree level
Synthetic organic chemistry is an area that has seen incredible growth through the years. The level of molecular complexity that can be achieved through available synthetic methods today is remarkable. Still, as the field continues to progress, increasing focus is being placed upon the strategic development of methods that are both efficient and selective in order to allow for the rapid assembly of molecular complexity. In this regard, organoboron reagents represent a class of compounds that have demonstrated great synthetic diversity. These compounds have been applied, through a range of methods, in the efficient construction of C-heteroatom and C-C bonds. Arguably among some of the most frequently used processes is the Suzuki-Miyaura cross-coupling. Since its conception, this reaction has been widely applied in a broad range of fields including, but not limited to, the pharmaceutical and materials industries. To date, the application of the Suzuki-Miyaura cross-coupling to the construction of sp2-sp2 bond connections has been extensively studied and many groups are now directing efforts towards employing this method for the construction of stereogenic centres. To this end, this thesis details studies in developing catalytic stereoselective Suzuki-Miyaura reactions for the cross-coupling of sp3-hybridized organoboronates for the efficient construction of stereogenic carbon centres. In order to demonstrate the versatility of optically enriched diboronyl compounds, Chapter 2 describes the development of an iterative cross-coupling process to transform 3,3-diboronylamides into the corresponding diarylmethanes – a motif that is commonly found in pharmaceutically relevant compounds. In addition, studies were made to determine the stereochemical outcome of the cross-coupling reaction. As a progression from the cross-coupling of optically enriched secondary boronates, Chapter 3 describes the development of an asymmetric Suzuki-Miyaura cross-coupling reaction for the desymmetrization of prochiral 1,1-diboronylalkanes. Ligand optimization in combination with mechanistic studies on the role of the base led to reaction conditions that produced optically enriched secondary organoboronates in good yields and enantioselectively. The details of the reaction scope and scalability will also be discussed. Due to the synthetic value demonstrated by 1,1-diboronyl compounds, an extension of these cross-coupling methods to 1,1,1-triboronylated compounds is desirable, as this would represent a unique way to construct complex stereogenic centres. In Chapter 4, initial studies on the synthesis of 1,1,1-triboronyl alkanes will be described. Given their similar potential as a synthetic handle for the construction of stereogenic centres, the development of a method that produces 3,3-diboronyl 3-silyl ketones as the products will also be discussed.
Permission is hereby granted to the University of Alberta Libraries to reproduce single copies of this thesis and to lend or sell such copies for private, scholarly or scientific research purposes only. The author reserves all other publication and other rights in association with the copyright in the thesis and, except as herein before provided, neither the thesis nor any substantial portion thereof may be printed or otherwise reproduced in any material form whatsoever without the author's prior written permission.
Citation for previous publication
Sun, H.-Y.; Hall, D. G. “At the Forefront of the Suzuki-Miyaura Reaction: Advances in Stereoselective Cross-Couplings”, book chapter in “Topics in Organometallic Chemistry: Synthesis and Application of Organoboron Compounds” (Eds. Fernandez, E. & Whiting, A), Springer, Heidelberg, 2014.Lee, J. C. H.; Sun, H.-Y.; Hall, D. G. “Optimization of Reaction and Substrate Activation in the Stereoselective Cross-Coupling of Chiral 3,3-Diboronyl Amides” J. Org. Chem. 2015, 80, 7134-7143.Sun, H.-Y.; Kubota, K.; Hall, D. G. “Optimization of Ligand, Scalability, and Mechanistic Insights on the Catalytic Enantioselective Desymmetrization of 1,1-Diboronylalkanes via Suzuki-Miyaura Cross-Coupling” Chem. Eur. J. 2015, in press. (DOI: 10.1002/chem.201406680).

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