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Applications of Nickel-Catalyzed Cross-Coupling Methods in the Synthesis of Organofluorine Compounds


Liang, Yufan (2016) Applications of Nickel-Catalyzed Cross-Coupling Methods in the Synthesis of Organofluorine Compounds. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9CF9N45.


The applications of nickel-catalyzed cross-coupling strategy to the synthesis of organofluorine compounds are explored in this thesis.

Chapter 2 describes the development of the first enantioselective cross-coupling method using secondary geminal dihalides as electrophiles. This method provides a unique approach for the generation of enantioenriched tertiary alkyl fluorides. These cross-coupling products can be further transformed into a variety of potentially valuable chiral building blocks.

Chapter 3 describes the development of a practical and versatile Negishi alkylation method employing α-halo-α-perfluoroalkyl secondary electrophiles. Target molecules bearing perfluoroalkyl-substituted (including trifluoromethyl-substituted) tertiary carbons can be easily generated from fluorinated electrophiles. Competition experiments and mechanistic studies have been performed to reveal the unique properties of these electrophiles and also prove the existence of alkyl radicals.

Chapter 4 describes the development of an asymmetric Negishi arylation protocol with α-halo-α-trifluoromethyl secondary electrophiles. This study provides a unique approach to construct trifluoromethyl-substituted tertiary stereocenters. The optimized condition can also be directly applied to substrates bearing an array of fluoroalkyl groups.

Chapter 5 details the progress towards the development of an asymmetric alkynylation method employing α-halo-α-trifluoromethyl secondary electrophiles. Preliminary studies also demonstrate that the protocol we developed has the potential to be used for other non-fluorinated secondary electrophiles.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:nickel; cross-coupling; fluorine; asymmetric catalysis
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Awards:The Herbert Newby Mccoy Award, 2016
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Fu, Gregory C.
Thesis Committee:
  • Grubbs, Robert H. (chair)
  • Peters, Jonas C.
  • Stoltz, Brian M.
  • Fu, Gregory C.
Defense Date:26 February 2016
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
Record Number:CaltechTHESIS:03012016-104838419
Persistent URL:
Related URLs:
URLURL TypeDescription related to Chapter 2 related to Chapter 3 related to Chapter 4
Liang, Yufan0000-0002-0533-2982
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9596
Deposited By: Yufan Liang
Deposited On:09 Mar 2017 17:28
Last Modified:04 Oct 2019 00:12

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