Development of Cu-Catalyzed Decarboxylative Heteroarylation and Rh-Catalyzed Carbene Olefination

• Author / Creator

  Yin, Shengkang

• Transition metal-catalyzed cross-coupling reactions are widely used transformations to generate useful chemicals. The development of new variants for transition metal-catalyzed cross-coupling reactions provides more efficient methods for the construction of functionalized molecules. This thesis describes the study of two novel transition metal-catalyzed cross-coupling processes. Chapter 1 describes the decarboxylative cross-coupling of malonic acid derivatives and heteroarylboronic esters. The use of oxidative Cu catalysis enables the synthesis of monoheteroaryl acetate derivatives containing electrophilic functional groups under mild conditions. This heteroarylation transformation provides a new route for late-stage functionalization for the preparation of drugs. The reaction development and the scope of both malonic acid derivatives and heteroarylboronic esters are detailed. The discovery of a Z-favored Rh-catalyzed olefination between diazo esters and iodonium electrophiles is discussed in Chapter 2. This reaction exhibits complementary stereoselectivity to the established E-alkene synthesis via Pd-catalyzed carbene cross-coupling. The preliminary optimization results of the Rh-catalyzed olefination are summarized.

• Subjects / Keywords

  • Decarboxylative heteroarylation
  • Carbene olefination

• Graduation date

  Fall 2017

• Type of Item

  Thesis

• Degree

  Master of Science

• DOI

  https://doi.org/10.7939/R3VX06K20

• License

  This thesis is made available by the University of Alberta Libraries with permission of the copyright owner solely for non-commercial purposes. This thesis, or any portion thereof, may not otherwise be copied or reproduced without the written consent of the copyright owner, except to the extent permitted by Canadian copyright law.