Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods
Authors: Cheng, Gui-Juan
Free Preview- Nominated as an outstanding PhD thesis by Peking University
- Combines ion mobility mass spectrometry and computational chemistry to investigate reaction mechanisms in catalysis
- Provides mechanistic insights for a broad range of important C-H activation reactions
- Establishes a universal chirality-relay model for Pd/mono-N-protected amino acid (MPAA)-catalyzed asymmetric C-H activation reactions
Buy this book
- About this book
-
This thesis presents detailed mechanistic studies on a series of important C-H activation reactions using combined computational methods and mass spectrometry experiments. It also provides guidance on the design and improvement of catalysts and ligands. The reactions investigated include: (i) a nitrile-containing template-assisted meta-selective C-H activation, (ii) Pd/mono-N-protected amino acid (MPAA) catalyzed meta-selective C-H activation, (iii) Pd/MPAA catalyzed asymmetric C-H activation reactions, and (iv) Cu-catalyzed sp3 C-H cross-dehydrogenative-coupling reaction.
The book reports on a novel dimeric Pd-M (M = Pd or Ag) model for reaction (i), which successfully explains the meta-selectivity observed experimentally. For reaction (ii), with a combined DFT/MS method, the author successfully reveals the roles of MPAA ligands and a new C-H activation mechanism, which accounts for the improved reactivity and high meta-selectivity and opens new avenues for ligand design. She subsequently applies ion-mobility mass spectrometry to capture and separate the [Pd(MPAA)(substrate)] complex at different stages for the first time, providing support for the internal-base model for reaction (iii). Employing DFT studies, she then establishes a chirality relay model that can be widely applied to MPAA-assisted asymmetric C-H activation reactions. Lastly, for reaction (iv) the author conducts detailed computational studies on several plausible pathways for Cu/O2 and Cu/TBHP systems and finds a reliable method for calculating the single electron transfer (SET) process on the basis of benchmark studies.
- Table of contents (5 chapters)
-
-
General Introduction
Pages 1-41
-
Mechanistic Studies on Pd(OAc)2-Catalyzed Meta-C–H Activation Reaction
Pages 43-62
-
Mechanistic Studies on Pd(MPAA)-Catalyzed Meta- and Ortho-C–H Activation Reactions
Pages 63-81
-
Mechanistic Studies on Pd(MPAA)-Catalyzed Enantioselective C–H Activation Reactions
Pages 83-110
-
Mechanistic Studies on Copper-Catalyzed sp3-C–H Cross-Dehydrogenative Coupling Reaction
Pages 111-126
-
Table of contents (5 chapters)
- Download Sample pages 2 PDF (958.8 KB)
- Download Table of contents PDF (127.6 KB)
Recommended for you
Bibliographic Information
- Bibliographic Information
-
- Book Title
- Mechanistic Studies on Transition Metal-Catalyzed C–H Activation Reactions Using Combined Mass Spectrometry and Theoretical Methods
- Authors
-
- Gui-Juan Cheng
- Series Title
- Springer Theses
- Copyright
- 2017
- Publisher
- Springer Singapore
- Copyright Holder
- Springer Nature Singapore Pte Ltd.
- eBook ISBN
- 978-981-10-4521-9
- DOI
- 10.1007/978-981-10-4521-9
- Hardcover ISBN
- 978-981-10-4520-2
- Softcover ISBN
- 978-981-13-5157-0
- Series ISSN
- 2190-5053
- Edition Number
- 1
- Number of Pages
- XVII, 126
- Number of Illustrations
- 18 b/w illustrations, 77 illustrations in colour
- Topics
