Alexandria Digital Research Library

Development of gold-catalyzed insertions into unactivated aliphatic C-H bonds

Author:
Wang, Youliang
Degree Grantor:
University of California, Santa Barbara. Chemistry
Degree Supervisor:
Liming Zhang
Place of Publication:
[Santa Barbara, Calif.]
Publisher:
University of California, Santa Barbara
Creation Date:
2016
Issued Date:
2016
Topics:
Chemistry
Keywords:
Gold Vinylidene
Gold Carbene
C-H Functionalization
Gold Catalysis
Gold Benzyne
Organic Chemistry
Genres:
Dissertations, Academic and Online resources
Dissertation:
Ph.D.--University of California, Santa Barbara, 2016
Description:

Despite the tremendous advance in homogeneous gold catalysis in the past decade or so, the functionalization of unactivated C(sp3)-H bonds, a highly desirable and yet challenging streamlining synthetic strategy, has so far rarely been realized in this 'gold rush'. My graduate work was focused on the development of new strategies of gold catalysis to access highly reactive gold intermediates and harness their reactivities in insertion into unactivated C(sp3)-H bonds. Three approaches are discussed in this dissertation: (1) via gold vinylidenes: fully functionalized gold vinylidenes generated from simple TMS-terminated alkynones facilely insert into unactivated alkyl groups to furnish versatile 2-bromocyclopentenones; (2) via 'gold benzyne': gold-catalyzed cycloisomerizations of enediynes provide access to hypothetical 'gold benzyne' species, which exhibit reactivities distinctively different from transition metal-free benzynes, including insertions into unactivated C(sp3)-H bonds and regiospecific nucleophilic additions; (3) via oxidatively generated gold carbene: gold carbenes generated upon the oxidation of alkynones are demonstrated for the first time to be capable of inserting into unactivated C(sp 3)-H bonds to yield cylcopentanones and cyclobutanones.

Physical Description:
1 online resource (241 pages)
Format:
Text
Collection(s):
UCSB electronic theses and dissertations
ARK:
ark:/48907/f3hh6k72
ISBN:
9781369340693
Catalog System Number:
990047190160203776
Rights:
Inc.icon only.dark In Copyright
Copyright Holder:
Youliang Wang
File Description
Access: Public access
Wang_ucsb_0035D_13165.pdf pdf (Portable Document Format)