Investigating Sustainable Precious Metal Catalysis: Routine Dirhodium Catalyzed Carbene Reactions with High Yield and Enantioselectivity at Low Loadings Open Access

Chuba, Matthew David (2016)

Permanent URL: https://etd.library.emory.edu/concern/etds/w6634378j?locale=en
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Abstract

Precious metal catalysts have been established to have highly desirable reactivity and selectivity profiles in carbene reactions. Three approaches have emerged to make this transformation more sustainable: reproducing the reaction with earth abundant catalysts, improving recyclability through immobilization of the precious metal catalysts and optimizing the reaction of the precious metal catalysts. This project focuses on the last approach, an avenue the findings of which is expected to have significant impact on the previous two. To date, our investigations have focused on developing routine conditions that provide high yields and enantioselectivity in carbene reactions such as cyclopropanation and C-H functionalization reactions. Using methyl 2-furoate as a model substrate, we were able to demonstrate that cyclopropanation can be performed reproducibly with TONs close to 2 million employing loadings as low as 0.00005 mol% of Rh2(S-TCPTTL)4. Using 0.001 mol% of Rh2(S-TCPTTL)4 as the optimum catalyst loading, cyclopropanation and C-H insertion reactions were performed on a variety of substrates demonstrating the robustness of the developed conditions.

Table of Contents

Introduction...................................1

Results and Discussion...................10

Conclusion and Future Work............31

References...................................34

Experimental................................35

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