Pan, Xiangcheng
(2014)
CHEMISTRY AND APPLICATIONS OF N-HETEROCYCLIC CARBENE BORANES.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
Abstract
Chemistry and applications of N-heterocyclic carbene borane complex are demonstrated. Chapter 1 describes and introduces the background of NHC-boranes. Chapter 2 demonstrates the discovery and studies of thiol-catalyzed radical reduction reactions of alkyl and aryl halides with NHC-boranes. The radical reductive cyclization reactions with NHC-boranes were also investigated. These reactions occur by a polarity-reversal process, where thiol is the polarity-reversal catalysis. Chapter 3 describes the development and preparative experiments of first homolytic substitution reactions of NHC-boryl radicals at divalent atoms such as sulfur and selenium. The primary reaction products of heterocycle disulfides undergo a 1,3-boryl shift from S to N to give new class of stable NHC-boranes with B-N heterocycles bonds.
Chapter 4 describes the discovery that disulfides (RSSR), NHC-boryl mono- (NHC-BH2SR) and bis-sulfides (NHC-BH(SR)2) serve as both radical initiators and precatalysts in the radical reductions and reductive cyclizations with NHC-boranes. These reactions are also believed to occur by the polarity reversal catalysis mechanism. Chapter 5 describes the thiolation reactions with new synthesized NHC-boryl sulfides and –amido complexes. Chapter 6 introduces iodine-activated hydroboration and preliminary results of direct hydroboration.
Share
| Citation/Export: |
|
| Social Networking: |
|
Details
| Item Type: |
University of Pittsburgh ETD
|
| Status: |
Unpublished |
| Creators/Authors: |
|
| ETD Committee: |
|
| Date: |
24 September 2014 |
| Date Type: |
Publication |
| Defense Date: |
27 May 2014 |
| Approval Date: |
24 September 2014 |
| Submission Date: |
30 May 2014 |
| Access Restriction: |
No restriction; Release the ETD for access worldwide immediately. |
| Number of Pages: |
202 |
| Institution: |
University of Pittsburgh |
| Schools and Programs: |
Dietrich School of Arts and Sciences > Chemistry |
| Degree: |
PhD - Doctor of Philosophy |
| Thesis Type: |
Doctoral Dissertation |
| Refereed: |
Yes |
| Uncontrolled Keywords: |
NHC, carbene, borane, radical |
| Date Deposited: |
24 Sep 2014 17:42 |
| Last Modified: |
15 Nov 2016 14:20 |
| URI: |
http://d-scholarship.pitt.edu/id/eprint/21714 |
Metrics
Monthly Views for the past 3 years
Plum Analytics
Actions (login required)
 |
View Item |
![[feed]](/images/feed-icon-32x32.png){kind=icon}