Asymmetric Functionalization of C-H Bonds

430 Pages·2015·32.504 MB·English

by  Shu-Li You, Chris Hardacre

Asymmetric Functionalization of CeH Bonds
RSC Catalysis Series
Editor-in-Chief:
Professor Chris Hardacre, Queen’s University Belfast, Northern Ireland, UK
Series Editors:
Professor Bert Klein Gebbink, Utrecht University, The Netherlands
Professor Jose Rodriguez, Brookhaven National Laboratory, USA
Titles in the Series:
1: Carbons and Carbon Supported Catalysts in Hydroprocessing
2: Chiral Sulfur Ligands: Asymmetric Catalysis
3: Recent Developments in Asymmetric Organocatalysis
4: Catalysis in the Refining of Fischer–Tropsch Syncrude
5: O rganocatalytic Enantioselective Conjugate Addition Reactions:
A Powerful Tool for the Stereocontrolled Synthesis of Complex
Molecules
6: N -Heterocyclic Carbenes: From Laboratory Curiosities to Efficient
Synthetic Tools
7: P-Stereogenic Ligands in Enantioselective Catalysis
8: Chemistry of the Morita–Baylis–Hillman Reaction
9: P roton-Coupled Electron Transfer: A Carrefour of Chemical Reactivity
Traditions
10: Asymmetric Domino Reactions
11: CeH and CeX Bond Functionalization: Transition Metal Mediation
12: Metal Organic Frameworks as Heterogeneous Catalysts
13: Environmental Catalysis Over Gold-Based Materials
14: Computational Catalysis
15: Catalysis in Ionic Liquids: From Catalyst Synthesis to Application
16: Economic Synthesis of Heterocycles: Zinc, Iron, Copper, Cobalt,
Manganese and Nickel Catalysts
17: Metal Nanoparticles for Catalysis: Advances and Applications
18: Heterogeneous Gold Catalysts and Catalysis
19: Conjugated Linoleic Acids and Conjugated Vegetable Oils
20: Enantioselective Multicatalysed Tandem Reactions
21: New Trends in Cross-Coupling: Theory and Applications
22: Atomically-Precise Methods for Synthesis of Solid Catalysts
23: Nanostructured Carbon Materials for Catalysis
24: H eterocycles from Double-Functionalized Arenes: Transition
Metal Catalyzed Coupling Reactions
25: Asymmetric Functionalization of CeH Bonds
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Asymmetric Functionalization
e
of C H Bonds
Edited by
Shu-Li You
Shanghai Institute of Organic Chemistry,
Chinese Academy of Sciences, Shanghai, China
Email: [email protected]
RSC Catalysis Series No. 25
Print ISBN: 978-1-78262-102-7
PDF eISBN: 978-1-78262-196-6
ISSN: 1757-6725
A catalogue record for this book is available from the British Library
© The Royal Society of Chemistry 2015
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Foreword
The notion of cleaving strong and seemingly inert CeH bonds has been a
concept that has intrigued and inspired chemists for nearly a century. The
fundamental reactivity and rich mechanistic implication of metal insertion
into CeH bonds has attracted chemists from different fields into a wonder-
land of opportunity since the 1970s. Over the past several decades, subse-
quent functionalization of such carbon–metal species were made catalytic,
and various redox catalytic cycles are now established to deliver synthetically
relevant, diverse transformations. Most recently, the ability to perform CeH
activation reactions on abundant and broadly useful substrates represents
another major step forward towards widespread adoption of CeH activation
reactions in organic synthesis. However, for CeH activation to impact asym-
metric synthesis, general and efficient asymmetric CeH activation reactions
must be developed.
Strictly speaking, asymmetric CeH functionalization reactions refer to those
transformations in which the newly defined stereochemistry is controlled
by the CeH cleavage step. For example: the carbene, nitrene, and metal-oxo
chemistry, as well as the organometallic metal insertion chemistry, have been
demonstrated to perform asymmetric CeH activation in this manner. Gen-
erally, a new chiral center is created by cleaving a prochiral CeH bond (with
the exception of atroposelective CeH cleavage or kinetic resolution via CeH
activation). In the interests of readers and practitioners, however, the authors
have taken a broader view and included other types of asymmetric transforma-
tions that involve CeH cleavage as one of the non-enantio determining steps.
Notably, functionalization of highly acidic or weak CeH bonds adjacent to
heteroatoms are also discussed. Indeed this approach allows for the inclusion
of a larger number of important asymmetric processes and showcases how
CeH activation can be connected to asymmetric catalysis. Comprehensive
RSC Catalysis Series No. 25
Asymmetric Functionalization of CeH Bonds
Edited by Shu-Li You
© The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org
vii
viii Foreword
discussions on a broad range of approaches adopted in asymmetric catalysis
based on CeH activation chemistry greatly enrich this book and will benefit
the readers tremendously.
In conclusion, asymmetric CeH functionalization has emerged as a new
avenue for developing asymmetric catalysis and will create practical and
enabling synthetic disconnections for asymmetric synthesis in the foresee-
able future. This fine book comprehensively details the historic development
and state-of-the-art of asymmetric CeH functionalization processes. Various
different types of approaches or transformations are also meticulously cate-
gorized to improve readability. I anticipate that this book will be a popular
and insightful tool for those who are interested in this rapidly rising and yet
underdeveloped field.
Jin-Quan Yu
La Jolla, California
Preface
This book will focus on direct asymmetric CeH bond functionalization reac-
tions. The direct functionalization of inert CeH bonds is of great importance
in modern synthetic chemistry since it can employ the readily available hydro-
carbons (or any CeH bond-containing compounds) as the starting material
to construct the molecular complexity without “pre-activation” of the CeH
bonds and thus meets the criteria of atom economy and step economy.
Among all the great challenges that accompany the CeH bond functional-
ization process, one of the most significant challenges is how to distinguish
the reactivity among the numerous CeH bonds in one single molecule and
achieve the versatile transformations in a highly efficient way. In recent
years, several novel types of methodology have emerged for the direct enan-
tioselective functionalization of inert CeH bonds by chiral organometallic
complexes or organocatalysts. In general, these novel reactions point out
a promising direction for the development of the next generation of asym-
metric synthesis. The emerging methods for direct asymmetric functional-
ization of inert CeH bonds reveal novel reactivity of fundamental chemical
feedstocks. The deep understanding of their mechanisms is beneficial for
the design and development of highly efficient chiral catalytic systems appli-
cable for asymmetric catalysis. In addition, these reactions provide unprece-
dented retro-synthetic disconnection strategies for the synthesis of complex
targets and will definitely stimulate further advances in organic chemistry.
My personal interest in asymmetric catalysis can be dated back to my grad-
uate study under the supervision with Professor Li-Xin Dai at the Shanghai
Institute of Organic Chemistry, where my Ph.D. thesis had been focused on
the synthesis of (planar) chiral ferrocene ligands and their application in
Pd-catalyzed allylic substitution reactions. Since my independent research
was started in 2006, our group has been focusing on asymmetric direct
functionalization reactions of various CeH bonds, including Pd-catalyzed
RSC Catalysis Series No. 25
Asymmetric Functionalization of CeH Bonds
Edited by Shu-Li You
© The Royal Society of Chemistry 2015
Published by the Royal Society of Chemistry, www.rsc.org
ix
x Preface
asymmetric synthesis of planar chiral ferrocenes via CeH bond function-
alization reactions, asymmetric Friedel–Crafts type reactions, and N-het-
erocyclic carbene (NHC) catalyzed aldehyde CeH bond functionalization.
Through the years, I have been amazed by the fast development of this field.
The asymmetric CeH bond direct functionalization reactions have emerged
very rapidly in the last decade and now receive increasing attention in the
areas of organic chemistry, medicinal chemistry, materials science, and
many more. There are quite a few review articles covering this fast growing
field.1 Our motivation to write a book on the topic of asymmetric CeH bond
functionalization reactions originated from the time when we wrote a review
on such a topic.2 It is amazing to see the fast development of this field; there
have been many new papers published during every stage of the production
of that review, such as submission, revision and proof. On the other hand,
despite these existing reviews, many of them were written with the focus on
one subject of the asymmetric CeH bond functionalization reactions. A com-
prehensive review covering the whole field has not appeared yet. In addition,
given the rapidly increased number of papers in this field, it is not possible
to cover it within one review article. A book summarizing the origin, mecha-
nism, scope, and application of the asymmetric CeH bond functionalization
reaction should be timely and highly useful.
The nine chapters of this book have been designed to cover the major-
ity of asymmetric CeH bond functionalization reactions. In the Chapter 1,
asymmetric insertion reactions into CeH bonds by metal carbenoids, metal
nitrenoids, and metal-oxo species are summarized. This kind of reaction is
probably the more traditional (or earlier) method to realize asymmetric CeH
bond functionalization. The results are classified according to carbene (or
equivalents) precursors such as metal carbenoids, metal nitrenoids, and met-
al-oxo species. The application of these methods in total synthesis are also
briefly discussed. In Chapter 2, asymmetric cross-dehydrogenative coupling
(CDC) reactions are discussed, offering a general picture of this powerful
method which could couple one C(sp3)eH bond α to a nitrogen, oxygen atom,
or a carbonyl group and various C(sp)eH, C(sp2)eH or C(sp3)eH bonds under
oxidative conditions. In Chapter 3, asymmetric oxidative biaryl coupling
reactions are introduced in detail as they provide the most atom-economical
way to synthesize axially chiral biaryl compounds. In Chapter 4, we have sum-
marized the asymmetric [1,5]-hydride transfer reactions, which represent an
important method to realize the asymmetric functionalization of C(sp3)eH
bonds in a redox-neutral fashion. Both transition metal complexes and small
molecule organocatalyst-catalyzed transformations are introduced. In Chap-
ter 5, asymmetric CeH bond functionalization involving a transient CeM
(carbon–metal) species is summarized. The asymmetric CeH bond function-
alization involving a transient MeC species has witnessed significant devel-
opment in recent years. Various transition metal complexes are found capable
of promoting the reactions. Compared with traditional cross-coupling reac-
tions, these transformations do not require pre-activation and lead to less
salt wastes. The discussion in this chapter is classified according to the metal
catalysts as well as the reaction mechanism. In Chapter 6, a brief overview on