Skip to main content
Duke University Libraries
DukeSpace Scholarship by Duke Authors
  • Login
  • Ask
  • Menu
  • Login
  • Ask a Librarian
  • Search & Find
  • Using the Library
  • Research Support
  • Course Support
  • Libraries
  • About
View Item 
  •   DukeSpace
  • Theses and Dissertations
  • Duke Dissertations
  • View Item
  •   DukeSpace
  • Theses and Dissertations
  • Duke Dissertations
  • View Item
JavaScript is disabled for your browser. Some features of this site may not work without it.

Zincative Functionalization of C–H Bonds Using Lithium Amide Zincate Bases

Thumbnail
View / Download
3.8 Mb
Date
2018
Author
Bitting, Katie Jane
Advisor
Wang, Qiu
Repository Usage Stats
276
views
85
downloads
Abstract

Carbon–hydrogen bond functionalization is a highly desirable transformation as C–H bonds are plentiful in feedstock chemicals and the direct introduction of valuable functional groups improves atom economy and efficiency. However, field of direct C–H functionalization still has many challenges including regioselectivity, directing group limitations, and often harsh reaction conditions with toxic and rare transition metal catalysts. Deprotonative zincation has been demonstrated as a useful method to achieve C–H functionalization.

The direct C–H amination of a wide scope of arenes and heteroarenes has been achieved by copper-catalyzed electrophilic amination with O-benzoyl hydroxylamines. Key to the expanded scope of substrates is the use of a lithium zincate base, Li[ZnEt2TMP] which can coordinate to a variety of common functionalities to direct zincation. The mild reaction conditions and compatibility with functional groups such as esters, nitriles and halides make this method orthogonal to many existing strategies.

Additionally, a novel lithium zincate base with inexpensive dicyclohexylamine has been developed and shown to be capable of efficient and regioselective zincation with an extensive scope of directing groups. Aryl and heteroaryl zincates can undergo direct electrophilic silylation and borylation without the need for any transition metal catalyst.

α-Functionalization of substituted amides and esters has been achieved by utilizing a tribasic lithium zincate for direct allylation and copper-catalyzed arylation and vinylation with aryl iodides and vinyl iodides. In summary, lithium zincate bases have been demonstrated to be broadly useful for diverse and regioselective C–H functionalization to introduce valuable complexity from simple starting materials.

Type
Dissertation
Department
Chemistry
Subject
Organic chemistry
Permalink
https://hdl.handle.net/10161/17496
Citation
Bitting, Katie Jane (2018). Zincative Functionalization of C–H Bonds Using Lithium Amide Zincate Bases. Dissertation, Duke University. Retrieved from https://hdl.handle.net/10161/17496.
Collections
  • Duke Dissertations
More Info
Show full item record
Creative Commons License
This work is licensed under a Creative Commons Attribution-Noncommercial-No Derivative Works 3.0 United States License.

Rights for Collection: Duke Dissertations


Works are deposited here by their authors, and represent their research and opinions, not that of Duke University. Some materials and descriptions may include offensive content. More info

Make Your Work Available Here

How to Deposit

Browse

All of DukeSpaceCommunities & CollectionsAuthorsTitlesTypesBy Issue DateDepartmentsAffiliations of Duke Author(s)SubjectsBy Submit DateThis CollectionAuthorsTitlesTypesBy Issue DateDepartmentsAffiliations of Duke Author(s)SubjectsBy Submit Date

My Account

LoginRegister

Statistics

View Usage Statistics
Duke University Libraries

Contact Us

411 Chapel Drive
Durham, NC 27708
(919) 660-5870
Perkins Library Service Desk

Digital Repositories at Duke

  • Report a problem with the repositories
  • About digital repositories at Duke
  • Accessibility Policy
  • Deaccession and DMCA Takedown Policy

TwitterFacebookYouTubeFlickrInstagramBlogs

Sign Up for Our Newsletter
  • Re-use & Attribution / Privacy
  • Harmful Language Statement
  • Support the Libraries
Duke University