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Pincer Compounds
Pincer Compounds
Chemistry and Applications

Edited by

David Morales-Morales
Instituto de Quı́mica, Universidad Nacional Autónoma de México, Mexico City, Mexico
Elsevier
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You were important at that time, you are important at this time,
you will be important forever.
My inspiration
Rodrigo and Leilani
List of Contributors
Matthew Asay, Instituto de Quı́mica Universidad
Nacional Autónoma de México, Mexico City, Mexico
Maravanji S. Balakrishna, Indian Institute
Technology Bombay, Powai, Mumbai, India
Wesley H. Bernskoetter, The University of Missouri,
Columbia, MO, United States
Benoı̂t Bertrand, University of East Anglia, Norwich,
United Kingdom
Manfred Bochmann, University of East Anglia, Norwich,
United Kingdom
Sarote Boonseng, University of Sussex,
Brighton, United Kingdom
Kristin Bowman-James, University of
Lawrence, KS, United States
Juan Cámpora, Instituto de Invetigaciones Quı́micas,
CSIC - Universidad de Sevilla, Seville, Spain
Daniel Canseco-González, Universidad Autónoma
Chapingo, Chapingo, Mexico
Ivan Castillo, Instituto de Quı́mica, Universidad
Nacional Autónoma de México, Mexico City, Mexico
Adrian B. Chaplin, University of Warwick, Coventry,
United Kingdom
Basujit Chatterjee, National Institute of Science
Education and Research, HBNI, Bhubaneswar, India
Xiangyang Chen, Institute of Chemistry, Chinese
Academy of Sciences, Beijing, PR China;; University
of Chinese Academy of Sciences Beijing, PR China
Gunanathan Chidambaram, National Institute of
Science Education and Research, HBNI, Bhubaneswar,
India
Jong-Hoo Choi, University of Cologne, Cologne,
Germany
Hans P. Cook, University of Warwick, Coventry, United
Kingdom
Hazel Cox, University of Sussex, Falmer, Brighton,
United Kingdom
Peng Cui, University of Notre Dame, Notre Dame, IN,
United States
of Jason A. Denny, Mississippi State University,
Mississippi State, MS, United States
Tara K.K. Dickie, University of Lethbridge, Lethbridge,
AB, Canada
Alejandro Dorazco-González, Centro Conjunto de
Investigación en Quı́mica Sustentable, UAEM-UNAM,
Toluca, Estado de México, México; Universidad
Nacional Autónoma de México, Mexico City, Mexico
Falmer, Libor Dostál, University of Pardubice, Pardubice, Czech
Republic
Kansas, Nathan A. Eberhardt, University of Cincinnati,
Cincinnati, OH, United States
Miguel A. Esteruelas, Departamento de Quı́mica
Inorgánica, Instituto de Sı́ntesis Quı́mica y Catálisis
Homogénea (ISQCH), Centro de Innovación en
Quı́mica Avanzada (ORFEO-CINQA), Universidad de
Zaragoza-CSIC, 50009 Zaragoza, Spain
Huaquan Fang, Chinese Academy of Sciences,
Shanghai, PR China
Julio Fernandez-Cestau, University of East Anglia,
Norwich, United Kingdom
Michael Findlater, Texas Tech University, Lubbock,
TX, United States
Jun-Fang Gong, Zhengzhou University, Zhengzhou, PR
China
Lucero González-Sebastián, Instituto de Quı́mica,
Universidad Nacional Autónoma de México, Mexico
City, Mexico
Nikolaus Gorgas, Vienna University of Technology,
Vienna, Austria
Hairong Guan, University of Cincinnati, Cincinnati,
OH, United States
Rajeev Gupta, University of Delhi, Delhi, India
Go Hamasaka, Institute for Molecular Science,
Myodaiji, Okazaki, Japan
xv
xvi List of Contributors

Paul G. Hayes, University of Lethbridge, Lethbridge, Pilar Palma, Instituto de Invetigaciones Quı́micas, CSIC -
AB, Canada Universidad de Sevilla, Seville, Spain
Nilay Hazari, Yale University, New Haven, CT, United Dennis Pingen, University of Konstanz, Konstanz,
States Germany
T. Keith Hollis, Mississippi State University, Mississippi Martin H.G. Prechtl, University of Cologne, Cologne,
State, MS, United States Germany
Zheng Huang, Chinese Academy of Sciences, Shanghai, Latchupatula Radhakrishna, Indian Institute of
PR China Technology Bombay, Powai, Mumbai, India
Kengo Hyodo, Ryukoku University, Otsu, Shiga, Japan Luca Rocchigiani, University of East Anglia, Norwich,
Vlad M. Iluc, University of Notre Dame, Notre Dame, United Kingdom
IN, United States Antonio Rodrı́guez-Delgado, Instituto de Invetigaciones
Jun-ichi Ito, Nagoya University, Nagoya, Japan Quı́micas, CSIC - Universidad de Sevilla, Seville,
Spain
Roman Jambor, University of Pardubice, Pardubice,
Czech Republic Gavin Roffe, University of Sussex, Falmer, Brighton,
United Kingdom
William D. Jones, University of Rochester, Rochester,
NY, United States Anu Saini, Texas Tech University, Lubbock, TX, United
States
Sandeep Kaur, University of Kansas, Lawrence, KS,
United States Eduardo Sola, Instituto de Sı́ntesis Quı́mica y Catálisis
Homogénea, CSIC Universidad de Zaragoza,
Karl Kirchner, Vienna University of Technology, Zaragoza, Spain
Vienna, Austria
Mao-Ping Song, Zhengzhou University, Zhengzhou, PR
Naveen V. Kulkarni, University of Rochester, China
Rochester, NY, United States
John Spencer, University of Sussex, Falmer, Brighton,
Pramod Kumar, University of Delhi, Delhi, India United Kingdom
Georgette M. Lang, Mississippi State University, Caroline M. Storey, University of Warwick, Coventry,
Mississippi State, MS, United States United Kingdom
Guixia Liu, Chinese Academy of Sciences, Shanghai, Yasuhiro Uozumi, Institute for Molecular Science,
PR China Myodaiji, Okazaki, Japan
Connor S. MacNeil, University of Lethbridge, Hugo Valdés, Universidad Nacional Autónoma de
Lethbridge, AB, Canada México, Mexico City, Mexico
Virginia Montiel-Palma, Centro de Investigaciones Jarl Ivar van der Vlugt, van ’t Hoff Institute for
Quı́micas, IICBA, Universidad Autónoma del Estado Molecular Sciences, University of Amsterdam,
de Morelos, Cuernavaca, Morelos, Mexico Amsterdam, The Netherlands
David Morales-Morales, Instituto de Quı́mica, Gerard van Koten, Utrecht University, Utrecht, The
Universidad Nacional Autónoma de México, Mexico Netherlands
City, Mexico
Ola F. Wendt, Lund University, Lund, Sweden
Shuichi Nakamura, Nagoya Institute of Technology,
Nagoya, Aichi, Japan Xinzheng Yang, Institute of Chemistry, Chinese
Academy of Sciences, Beijing, PR China;; University
Hisao Nishiyama, Nagoya University, Nagoya, Japan of Chinese Academy of Sciences Beijing, PR China
Montserrat Oliván, Departamento de Quı́mica Julio Zamora-Moreno, Centro de Investigaciones
Inorgánica, Instituto de Sı́ntesis Quı́mica y Catálisis Quı́micas, IICBA, Universidad Autónoma del Estado
Homogénea (ISQCH), Centro de Innovación en de Morelos, Cuernavaca, Morelos, Mexico
Quı́mica Avanzada (ORFEO-CINQA), Universidad de
Zaragoza-CSIC, 50009 Zaragoza, Spain Xinju Zhu, Zhengzhou University, Zhengzhou, PR
China
Preface

Ten years ago, The Chemistry of Pincer Compounds (Morales-Morales, David, and Jensen, Craig, Eds. 2007.
Burlington: Elsevier) came out from the need to collate the large and quickly growing information then available on
pincer compounds and their reactivities. At that time, Prof. Bill Jones wrote in his “Perspective and prospects for pincer
ligand chemistry” chapter, “Where are the developments for pincer chemistry going in the future? While prediction of
specific applications are speculative at best, it is clear that the pincer ligand will have a strong impact on future
research. The variability in the ligand structure is immense. . . Pincer ligands are here to provide an anchor for the future
of organometallic chemistry.” He was not mistaken as we can see from the 33 chapters in this book which cover a wide
variety of ligands, complexes, and applications. The evolution of pincer complexes has accompanied the evolution of
chemistry—for example, novel pincer compounds with earth abundant metals produce more environmentally benign
processes utilizing sustainable starting materials. Sustainable energy and greenhouse gases are extremely relevant issues
in scientific development which have been addressed by new pincer catalysts. These compounds have advanced our
knowledge in the production of hydrogen and the efficient use of molecules—such as CO2—as an abundant feedstock
to produce value-added products while simultaneously reducing atmospheric emissions. Small molecule activation is
another ongoing topic of research wherein pincer complexes have found relevant and cutting-edge uses. These are just
a few examples of the plethora of chemistry and authors gathered in this book. I extend my heartfelt gratitude to all my
colleagues that kindly and professionally accepted the invitation to share their chemistry research and made the time to
write a chapter for this book. I am sure this work will serve as an inspiration for others to continue future developments
in this interesting and pertinent area of pincer compounds.

David Morales-Morales
Instituto de Quı́mica, Universidad Nacional Autónoma de México, Mexico City, Mexico
Spring 2018

xvii
Chapter 1

Chiral Pincer Complexes for Asymmetric

Reactions
Jun-ichi Ito and Hisao Nishiyama
Nagoya University, Nagoya, Japan

Chapter Outline
1.1 Introduction 1 1.7 Allylation and Propargylation of Carbonyl Compounds 11
1.2 Reduction Reactions 1 1.8 Aldol and Mannich Reactions 13
1.3 Borylation Reactions 5 1.9 Hydrophosphination and Hydroamination 13
1.4 Alkynylation Reactions 6 1.10 Miscellaneous Reactions 16
1.5 Reactions with Carbenoids 7 1.11 Summary 17
1.6 Electrophilic Substitution Reactions 8 References 17

1.1 INTRODUCTION
Chiral pincer complexes have been widely utilized as active and selective catalysts in various asymmetric reactions in
organic synthesis. New chiral ligands and transition metal complexes have been designed to achieve high efficiency
and enantioselectivity. Among them, chiral NCN and PCP ligands A 2 C, containing a central phenyl backbone tethered
to two chiral units, have become popular (Scheme 1.1). These chiral pincer ligands were successfully employed to
develop transition metal catalysts for various asymmetric transformations, including alkylation, allylation, Diels Alder,
aldol, Michael, reductive-aldol, and hydrosilylation reactions. Related transformations were previously summarized by
Richards and Fossey in “The Chemistry of Pincer Compounds,” which was published in 2007 [1]. In this chapter, we
survey the subsequent development of chiral transition metal complexes with anionic pincer ligands for asymmetric
catalysis. In this context, bis(imidazoline) ligands B, which are among the most efficient ligands among chiral pincer
ligands, are described in Chapters 9 and 10, Transition Metal Pincer Complexes with Chiral Imidazoline Donor(s):
Synthesis and Asymmetric Catalysis and Chiral NCN Pincer-Type Catalysts Having Bis(imidazoline)s.

SCHEME 1.1 NCN- and PCP-pincer ligands.

1.2 REDUCTION REACTIONS

The asymmetric hydrogenation and hydrosilylation of unsaturated compounds, such as alkenes and ketones, are one of
the most versatile methods for the synthesis of chiral compounds. Previously, Nishiyama reported that NCN pincer Rh
complexes 1 containing chiral bis(oxazolinyl)phenyl ligands (Phebox) served as highly active and enantioselective cata-
lysts for the conjugate reduction of α,β-unsaturated carbonyl compounds, using (EtO)2MeSiH as the reducing agent [2].

Pincer Compounds. DOI: https://doi.org/10.1016/B978-0-12-812931-9.00001-3

© 2018 Elsevier Inc. All rights reserved. 1
2 Pincer Compounds

Although the acetate complexes 1 were moisture and air stable, the Rh(I) hydride active species were generated by the
reaction with hydrosilanes. This catalytic system was expanded to the conjugate reduction of bulky α,β-unsaturated
ketones 2, which produced 3 with high enantioselectivity (Scheme 1.2) [3]. In this reaction, the outcome of the absolute
configuration of 3 was significantly affected by the geometry of the CQC bond. Accordingly, E and Z-isomers, 2a and
2b, gave S and R-enantiomers 3, respectively. Furthermore, the catalytic loading could be reduced to 0.2 mol% without
loss of enantioselectivity. This reduction strategy mediated by an NCN pincer Rh complex was successfully employed
in a remote stereogenic control to construct an all-carbon quaternary center at the γ-carbonyl position (Scheme 1.2) [4].
Desymmetrizing reduction of one of the two CQC bonds in the γ,γ-disubstituted cyclohexadienone derivative 4
resulted in the formation of the corresponding 2-silyloxy diene 5, and this prevented over-reduction. Subsequent hydro-
lysis afforded the cyclohexenone derivative 6 with high enantioselectivity (93% ee).

SCHEME 1.2 Asymmetric conju-

gate reduction of α,β-unsaturated
carbonyl compounds catalyzed by
Rh acetate complexes.

Another application of NCN pincer complex 1a is the asymmetric hydrosilylation of disubstituted alkenes 7
(Scheme 1.3) [5]. The catalytic reaction of aromatic alkenes with (EtO)3SiH gave α-silylated products, which were con-
verted to corresponding chiral alcohols 8 in high yields and high enantioselectivities by successive Tamao oxidation. In
this reaction, both trans-alkene 7a and cis-alkene 7b afforded the same S-enantiomer 8a due to the rapid E/Z isomeriza-
tion of the CQC bond. Interestingly, dihydronaphthalene 7c exhibited β-selectivity, with inversion of configuration, to
give the α-hydroxylated product 8c (91% ee).

SCHEME 1.3 Asymmetric hydrosily-

lation of alkenes catalyzed by Rh ace-
tate complexes.

Asymmetric reduction of ketones to chiral alcohols is also an important transformation in organic synthesis. In
particular, the development of base-metal catalysts, such as Fe, is one of the most important topics in asymmetric
catalysis. Nishiyama applied an NNN pincer ligand bis(oxazolinylphenyl)amine (Bopa, 9a) [6] to the asymmetric
hydrosilylation of aromatic ketones with hydrosilanes catalyzed by the corresponding Fe and Co complexes, which
were generated in situ from Fe(OAc)2 and Co(OAc)2, respectively (Scheme 1.4) [7]. In particular, (EtO)2MeSiH was
found to be a suitable reducing agent. The enantioselectivity of the Co catalyst was found to be higher than that of
the Fe catalyst. The Bopa-Fe complex was isolated from the reaction of FeCl2 with 9a, where Fe(III) chloride
complex 10 was obtained via oxidation of Fe(II) to Fe(III) by air. In contrast, the reaction of 9a with Co(OAc)2
provided Bopa-Co(II) complex 11, in which the Bopa ligand acted as a neutral ligand without deprotonation of the
center NaH bond.
 Chiral Pincer Complexes for Asymmetric Reactions Chapter | 1 3

SCHEME 1.4 Asymmetric hydrosi-

lylation of ketones catalyzed by
Bopa-Fe and Co catalysts.

The Bopa-Fe system exhibited unique properties in the outcome of the absolute configuration of the obtained chiral
alcohols. The catalytic system was controlled by the presence of Zn metal as an additive (Scheme 1.5) [8]. When the
catalyst was prepared by pretreatment of Bopa-Fe chloride complex 10 with Zn, S-alcohols were obtained as the major
enantiomers with good enantioselectivities in the reaction of cyclic ketones. On the other hand, opposite R-enantiomers
were formed when using the catalyst generated from Bopa and Fe(OAc)2 in the absence of Zn metal.

SCHEME 1.5 Reversal of absolute configuration cat-

alyzed by Bopa-Fe catalysts.

Gade developed chiral pincer Fe catalysts using bis(2-pyridylimino)isoindoles, which were found to be attractive
scaffolds to construct chiral NNN pincer ligands. The (1)-2-carene derived ligand (Carbpi) was successfully utilized to
construct chiral pincer Fe complex 11, which showed high enantioselectivities in the asymmetric hydrosilylation of aro-
matic ketones with (EtO)2MeSiH. (Scheme 1.6) [9]. In this ligand system, introduction of bulky pentaphenyl substitu-
tion to the isoindole backbone effectively improved the enantioselectivities (up to 93% ee). It was proposed that a
potential backside attack of the substrate was blocked in the enantiomer-determining step.

SCHEME 1.6 Carbpi-Fe catalyzed asym-

metric hydrosilylation of ketones.

The combination of a bis(2-pyridylimino)isoindole framework with chiral oxazolines produces Boxmi-Fe complexes
12 and 13, which served as efficient catalysts in the asymmetric hydrosilylation of ketones (Scheme 1.7) [10]. Alkoxy
4 Pincer Compounds

complex 13, obtained by the reaction of 12 with (S)-1-phenyl-1-ethanol, showed high performance in the catalytic reac-
tion, giving chiral alcohols with high enantioselectivities (up to 99% ee).

SCHEME 1.7 Boxmi-Fe catalyzed asymmetric hydrosilylation of ketones.

Chiral NCN Fe complexes were also tested as catalysts for the hydrosilylation of ketones. Phebox-Fe bromide com-
plex 14 in the presence of Na(acac) was used in the catalytic hydrosilylation of ketones to give the corresponding chiral
alcohols with up to 66% ee (Scheme 1.8) [11]. The formation of chiral products suggested that the catalytic reaction
proceeded without decomposition of the NCN ligand framework. Silyl complex 15 exhibited catalytic activity in the
absence of a base but showed modest enantioselectivity [12]. In contract, stannyl complex 16 was less active than 15.

SCHEME 1.8 Phebox-Fe catalyzed asymmetric hydrosily-

lation of ketones.

The transfer hydrogenation reaction is a more practical method in the asymmetric reduction of ketones compared to
the hydrosilylation reaction. Baratta reported that chiral Ru complexes 17 containing monoanionic CNN pincer ligands
and Josiphos* ligand 19 (Josiphos* 5 (S,R)-1-{2-[Bis(4-methoxy-3,5-dimethylphenyl)phosphino]ferrocenyl}ethyldicy-
clohexylphosphine) served as highly efficient and enantioselective catalysts in the asymmetric transfer hydrogenation of
ketones using 2-propanol as reducing agent (Scheme 1.9) [13]. This catalytic reaction can be conducted under high sub-
strate/catalyst ratio (S/C) and TOF. Interestingly, 17 was also active in the asymmetric hydrogenation of ketones with
5 atm of H2 at 40 C, giving the corresponding chiral alcohols with high enantioselectivities (90% 2 99% ee) [14].
Furthermore, Os complex 18 displayed an improved catalytic activity compared to Ru analog 17 [15]. Combination of
18 with chiral phosphine 19 similarly provided an active and selective catalyst for both transfer hydrogenation and
hydrogenation of ketones.

SCHEME 1.9 Asymmetric transfer hydrogenation of ketones catalyzed by chiral CNN Ru and Os complexes.

NCN Pincer Ru complex 20 was used in the asymmetric hydrogenation and transfer hydrogenation of ketones
(Scheme 1.10) [16]. Complex 20 showed an interesting phenomenon regarding the enantioselectivity, which was
 Chiral Pincer Complexes for Asymmetric Reactions Chapter | 1 5

significantly improved by the addition of bulky chiral alcohols, such as (S)-1-(9-anthracenyl)ethanol (21), even in the
presence of large amounts of alcoholic solvents [17]. It was proposed that this result was caused by the strong interac-
tion between the Ru complex and the chiral bulky alcohol.

SCHEME 1.10 Asymmetric hydrogenation of ketones catalyzed by Phebox 2 Ru complex.

1.3 BORYLATION REACTIONS

The asymmetric addition of diboranes to unsaturated compounds has potential in organic synthesis due to the
high utility of the produced chiral borylated compounds, which can be stereospecifically converted into chiral
alcohols and amines. NCN-Rh acetate complex 1b exhibited high catalytic activity in the asymmetric conjugate
borylation of E-cinnamyl esters with B2pin2 to give the corresponding β-borylated compounds 22 in high
yields (Scheme 1.11) [18]. The successive oxidation with NaBO3 afforded β-hydroxy esters 23 with high
enantioselectivities (up to 97% ee). Interestingly, employing Z-cinnamyl esters gave 23 with the same absolute
configuration in 93% ee, indicating a quick isomerization of the Z-ester to E-ester. On the other hand, E and
Z-alkyl substituted acrylate derivatives provided the corresponding enantiomers based on the configuration of the
CQC bond. α,β-Unsaturated ketones and amides were also used in the borylation reaction, with good to high
enantioselectivities.

SCHEME 1.11 Asymmetric β-boration

of α,β-unsaturated carbonyl compounds
catalyzed by Phebox-Rh complex.

NCN-Rh complex 1a was used in the asymmetric diboration of alkenes with B2pin2, giving 1,2-diborane compounds
24 (Scheme 1.12) [19]. Oxidation by NaBO3
4H2O afforded chiral diols 25 with excellent enantioselectivities (up to
99% ee). The diboration of styrene could be performed with 0.1 mol% of catalyst without loss of enantioselectivity and
yield. The 11B NMR spectrum of the reaction mixture of 1a with B2pin2 showed the formation of a boryl Rh species,
which was suggested as an intermediate for the insertion to an alkene. This catalytic system was extended to the prepa-
ration of chiral 3-amino-1,2-propandiol derivatives by asymmetric diboration of N-protected allylamines and subsequent
oxidation in a one-pot procedure [20].

SCHEME 1.12 Asymmetric dibora-

tion of alkenes catalyzed by Phebox-
Rh complex.
6 Pincer Compounds

1.4 ALKYNYLATION REACTIONS

The asymmetric alkynylation of carbonyl compounds is a useful method for the synthesis of chiral propargyl alcohol deriva-
tives, which are the useful building blocks in organic synthesis. In particular, a simple catalytic reaction that avoids excess
amounts of activators, such as alkylzinc reagents, is attractive for the development of an atom-economical procedure. In this
context, Ohshima and Mashima described the high performance of Phebox-Rh complexes in the direct asymmetric alkyny-
lation of ketones (Scheme 1.13) [21]. After detailed optimization of the Phebox ligand structure, C1-symmetric Phebox
ligand 1d was found to be an efficient and selective catalyst in the direct alkynylation of α-ketoester 26 with terminal
alkynes, providing chiral propargylic alcohols 27 with high enantioselectivities (up to 99% ee). Furthermore, this catalytic
system was applied to the direct asymmetric alkynylation of α-ketiminoesters 28 [22]. In this reaction, C2-symmetric
Phebox-Rh complex 1c effectively produced propargylic amine derivatives 29. Regarding N-protecting groups, p-benzylox-
ycarbonyl (Cbz) derivatives 28 showed better result compared to p-toluenesulfonyl (Ts) and t-butoxylcarbonyl (Boc) deriva-
tives. On the basis of kinetic and density functional theory (DFT) studies in the alkynylation of α-ketiminoesters, the
authors proposed a reaction mechanism involving Rh alkynyl complexes 30, which were formed from the Phebox-Rh ace-
tate complex and a terminal alkyne [23]. Consequently, significant reaction rate enhancement was observed by using alky-
nyl complexes 30 as catalyst, which enabled not only to reduce the catalyst loading but also to expand the substrate scope.
For example, cyclic N-sulfonyl α-ketiminoesters 31 gave alkynylated compounds 32 with high enantioselectivity.

SCHEME 1.13 Asymmetric direct alkynylation of carbonyl compounds catalyzed by Phebox-Rh acetate complexes.

As an expansion of the utility of chiral pincer complexes in the asymmetric alkynylation of ketones, chiral CCN pin-
cer Rh acetate complexes 33 containing N-heterocyclic carbene and oxazoline hybrid ligands were tested (Scheme
1.14) [24]. The catalytic reaction of fluoroalkyl-substituted ketones with terminal alkynes afforded the corresponding
propargyl alcohols with high enantioselectivities (up to 93% ee). The stoichiometric reaction of 33b with PhCCH gave
monoalkynyl complex (CCN)Rh(k2-OAc)(CCPh), which reacted with another PhCCH molecule in the presence of pyri-
dine to give bisalkynyl complex (CCN)Rh(CCPh)2(py). Considering this result, bisalkynyl intermediate (CCN)Rh
(CCR)2 was proposed to be the active species for the insertion of the ketone into the Rh 2 alkynyl bond.

SCHEME 1.14 Asymmetric direct alkynylation of

ketones catalyzed by CCN-Rh acetate complexes.
 Chiral Pincer Complexes for Asymmetric Reactions Chapter | 1 7

NCN Ru acetate complex 35, containing a Phebox-type ligand, showed higher performance in the catalytic alkynyla-
tion of aldehydes than the Phebox-Rh analog (Scheme 1.15) [25]. The catalytic reaction proceeded in 2-propanol to
give chiral propargylic alcohols 36 with high enantioselectivities (up to 95% ee). In contrast to NCN-Rh complexes 1,
the alkynyl complex was not detected in the reaction with the Phebox-Ru catalyst. Complex 35 proved to be a good cat-
alyst for the conjugate addition of α,β-unsaturated carbonyl ketones, esters, amides, and phosphonates [26]. For exam-
ple, 3-penten-2-one gave the corresponding chiral product 37 with 82% ee.

SCHEME 1.15 Asymmetric direct alkynylation

of carbonyl compounds catalyzed by Phebox-Ru
acetate complexes.

Considering the results of the conjugate addition of alkynes to α,β-unsaturated ketones, a Ru-enolate species was
suspected as intermediate of the reaction. Trapping this enolate species by electrophiles, such as aldehydes, would be
a versatile method for the construction of complex molecules from simple starting materials. Ru complex 35
catalyzed the asymmetric three-component coupling reaction between terminal alkynes, α,β-unsaturated ketones, and
aldehydes in a one-pot procedure to give β-hydroxyketone derivatives 38, containing α-propargyl groups, in
high yields with moderate enantioselectivities (Scheme 1.16) [27]. A control experiment suggested that Ru-enolate
intermediate 39, generated by conjugate addition, was a key intermediate for the subsequent aldol reaction with
aldehydes.

SCHEME 1.16 Asymmetric three-component

coupling catalyzed by Phebox-Ru acetate
complexes.

1.5 REACTIONS WITH CARBENOIDS

An NCN Ir complex containing a Phebox ligand was synthesized by CaH activation of the Phebox ligand precursor
with an Ir chloride source, such as IrCl3
3H2O and H2IrCl6 [28]. Blakey reported Phebox-Ir complex 40 as an efficient
catalyst in the asymmetric CaH functionalization of 1,4-cyclohexadiene with phenyldiazoacetate derivatives (Scheme
1.17) [29]. The catalytic reaction proceeded with low catalyst loading to give the CaH inserted product 41 in high yield
and excellent enantioselectivity (up to 99% ee). The catalyst loading could be reduced to 0.5 mol% without the need of
slow addition or low temperature. DFT calculations revealed that the carbene ligand was coordinated with cis to the
Phebox plane in 42.
8 Pincer Compounds

SCHEME 1.17 Asymmetric CaH insertion catalyzed by

Phebox-Ir complex.

NCN Ru complexes 20 and 43 were found to be active and selective catalysts in the asymmetric cyclopropanation
of alkenes with a diazoester derivative, giving trans-cyclopropanes 44 (Scheme 1.18) [30]. Aqua complex 43 exhibited
high yield with high enantioselectivity. Its catalytic activity and enantioselectivity was found to be comparable to that
of the Pybox-Ru system, which had a neutral bisoxazoline tridentate ligand [31].

SCHEME 1.18 Asymmetric cyclopropa-

nation catalyzed by Phebox-Ru complex.

Gade reported that Boxmi-Co complex 45, containing the Carbpi ligand, served as a good catalyst in the asymmetric
intramolecular cyclopropanation to afford cyclopropanes 46 with up to 94% ee (Scheme 1.19) [9].

SCHEME 1.19 Asymmetric cyclopropa-

nation catalyzed by Carbpi-Co complex.

1.6 ELECTROPHILIC SUBSTITUTION REACTIONS

Gade has developed the Boxmi ligand for asymmetric catalysts in the electrophilic substitution of carbonyl compounds
via the abstraction of an activated α-hydrogen. The Boxmi-Ni catalyst, generated in situ from 47a and Ni
(ClO4)2
6H2O, was utilized in the asymmetric fluorination of oxindole derivatives 48 with N-fluorobenzenesulfona-
mide (NFSI) as fluorinating agent (Scheme 1.20) [32]. The fluorinated products 49 were obtained in high yields and
 Chiral Pincer Complexes for Asymmetric Reactions Chapter | 1 9

enantioselectivities. This catalytic system was also applied to the asymmetric fluorination of β-ketoesters with NFSI.
Isolation of Boxmi-Ni complex 50a was achieved from the reaction of 47a with NaH, followed by treatment with
NiCl2. Alternatively, the reaction of 47a with Ni(OAc)2 gave the acetate analog 50b.

SCHEME 1.20 Asymmetric fluorination of oxindoles catalyzed by

Boxmi-Ni complex.

Boxmi-Cu catalyst 51 was applied to the asymmetric alkylation of β-ketoesters with benzyl iodides and allyl iodides
(Scheme 1.21) [33]. In this reaction, the in situ generated Cu catalyst obtained by treatment of 47a with Cu(OAc)2
showed similar performance compared to the isolated complex 51. Benzyl and allyl iodides, generated in situ from the
reaction of benzyl and allyl alcohol with CsI and BF3
Et2O in MeCN, can be used for the alkylation reaction, enhanc-
ing the utility of this catalytic reaction. The proposed mechanism involved enolate intermediate 54 formed by coordina-
tion of 52 to a Cu center, followed by deprotonation with a base. Since the Si face of the Cu-enolate was blocked by
the Ph substituents of one of the oxazoline groups, the electrophile approached form the Re-face.

SCHEME 1.21 Asymmetric alkylation of

β-ketoesters catalyzed by Boxmi-Cu
complex.
10 Pincer Compounds

The application of the Boxmi-Cu catalyst was expanded to the asymmetric trifluoromethylation reaction of
β-ketoester derivatives (Scheme 1.22) [34]. Reaction of β-ketoester 52 with Togni’s reagent 55 in the presence of the
Boxmi-Cu catalyst, generated in situ by treatment of Cu(OTf)2 with BoxmiH 47a, provided the corresponding trifluoro-
methylated compounds 56 with high enantioselectivities. This catalytic system was applied to β-ketoesters 57, contain-
ing a six-membered cycle, which were effectively trifluoromethylated using Umemoto’s reagent 58 in the presence of a
base.

SCHEME 1.22 Asymmetric tri-

fluoromethylation reaction of
β-ketoesters catalyzed by Boxmi-
Cu complex.

The Boxmi-Cu system was also utilized in the asymmetric electrophilic trifluoromethylthiolation of β-ketoesters 52
using Lu and Shen’s SCF3-transfer reagent 60 (Scheme 1.23) [35]. β-Ketoesters having both five- and six-membered
cycles afforded the corresponding SCF3 substituted products 61. Since other metal salts, such as Fe(OCOEt)2, Ni
(ClO4)2
6H2O, and Zn(NTf)2, showed no asymmetric induction, the Cu catalyst was found to have an advantage in the
electrophilic transformation of β-ketoesters.

SCHEME 1.23 Asymmetric tri-

fluoromethylthiolation reaction of
β-ketoester catalyzed by Boxmi-
Cu complex.

The Boxmi-Fe catalyst 62 was employed in the asymmetric azidation of β-ketoesters 52 and oxindoles 48 (Scheme
1.24) [36]. The enantioselectivity was improved by the addition of silver carboxylate. In the case of the azidation of
oxindoles 48, the Fe catalyst generated in situ from Fe(OCOEt)2 and BoxmiH (47a) displayed higher enantioselectivity
than the catalyst generated from 62 and silver carboxylate, giving the corresponding azide oxindoles 64b.

SCHEME 1.24 Asymmetric azidation of β-ketoesters catalyzed by Boxmi-Fe complex.

 Chiral Pincer Complexes for Asymmetric Reactions Chapter | 1 11

As an application to Lewis acid catalysis, chiral Boxmi-Zn catalysts were utilized in the asymmetric allylation of oxi-
ndole derivatives 48 with allyl bromide, giving allylated products 65 with high enantioselectivities (Scheme 1.25) [37]. It
was found that the stoichiometric reaction of BoxmiH 47a with ZnEt2, followed by treatment with the oxindole, produced
zinc enolate complex 66, which reacted with allyl bromide to give 65 with high enantioselectivity (98% ee). The DFT calcu-
lation of the reaction with oxindoles showed that the lowest energy pathway was the Si-face attack in the square-pyramidal
geometry. In contrast, the use of Cu instead of Zn in this reaction gave racemic products 65 due to a radical mechanism.

SCHEME 1.25 Asymmetric allylation of oxindoles catalyzed by Boxmi-Zn complex.

1.7 ALLYLATION AND PROPARGYLATION OF CARBONYL COMPOUNDS

The asymmetric allylation and propargylation reactions of aldehydes were extensively explored by Nakada, where chi-
ral pincer Cr catalysts were generated in situ by treatment of Cr chloride with bis(oxazolinyl)carbazole ligands 66 [38].
This method, using Cr catalysts with chiral ligands 66, was applied to domino-type reactions. Connell reported that the
reaction of propargyl bromide derivatives 67 with aldehydes gave the corresponding allenylmethanols, which were trea-
ted with tetrabutylammonium fluoride (TBAF) to produce (1,3-butadienyl)methanols 68 (Scheme 1.26) [39]. Zhang
used 2-(bromomethyl) acrylates 69 in the Cr-catalyzed allylation of aldehydes [40]. The successive lactonization cata-
lyzed by acid produced chiral α-exo-methylene γ-butyrolactones 70 with high enantioselectivities of up to 99% ee.

SCHEME 1.26 Domino-type

transformation by using allyla-
tions and propargylations.

The asymmetric addition of 2-(chloromethyl)benzofuran 71 to aldehydes catalyzed by a Cr catalyst containing the

ethyl analog of 66 gave the corresponding dearomatized products 72a in high yields (Scheme 1.27) [41]. The use of 66
and Cp2ZrCl2 improved the selectivity for 72a and decreased the yield of byproducts 72b. This reaction was applied to
2-(chloromethyl)benzothiophene and 2-chloromethyl indene derivatives.
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left near the trap standing up against a tree, and
Dave ran up and grabbed it and struck the animal on
the head and cut his throat. How we did laugh and
dance around that defunct porker. Exciting sport this
trapping for fresh pork. In half an hour Dave and Eli
had the pig skinned and dressed. Is not a large one
probably weighs ninety pounds or so, and is fat and
nice. Have sliced up enough for about a dozen men
and are now cooking it on sticks held up before the
fire. Also frying some in a skillet which we are the
possessor of. When the hogs run wild and eat
acorns, roots and the like, the meat is tough and
curly but is sweet and good. We fry out the grease
and then slice up the potatoes and cook in it. Thanks
to Mr. Kimball we have plenty of salt to season our
meat with. The buzzards are after their share which
will be small. And now it is most night again and the
“Astor House” larder is full. Seems too bad to go to
bed with anything to eat on hand, but must. That is
the feeling with men who have been starved so long,
cannot rest in peace with food laying around. My two
comrades are not so bad about that as I am, having
been well fed for a longer period. Have sat up three
or four hours after dark, talking over what we will do
when we get home, and will now turn in for a sound
sleep. It’s a clear moonlight night, and we can hear
very plain a long distance. Can also see the light
shining from camp fires in many directions, or what
we take to be such.
Dec. 22.—As Dan Rice used to say in the circus
ring: “Here we are again.” Sleep so sound that all the
battles in America could not wake me up. Are just
going for that fresh pork to-day. Have three kinds of
meat—fried pig, roast pork and broiled hog. Good
any way you can fix it. Won’t last us three days at
this rate, and if we stay long enough will eat up all
the hogs in these woods. Pretty hoggish on our part,
and Dave says for gracious sake not to write down
how much we eat, but as this diary is to be a record
of what takes place, down it goes how much we eat.
Tell him that inasmuch as we have a preacher along
with us, we ought to have a sermon occasionally.
Says he will preach if I will sing, and I agree to that if
Eli will take up a collection. One objection Eli and I
have to his prayers is the fact that he wants the
rebels saved with the rest, yet don’t tell him so.
Mutually agree that his prayers are that much too
long. Asked him if he thought it stealing to get those
potatoes as I did, and he says no, and that he will go
next time. We begin to expect the Yankees along. It’s
about time. Don’t know what I shall do when I again
see Union soldiers with guns in their hands, and
behold the Stars and Stripes. Probably go crazy, or
daft, or something. This is a cloudy, chilly day, and
we putter around gathering up pine knots for the fire,
wash our duds and otherwise busy ourselves. Have
saved the hog skin to make moccasins of, if the
Union army is whipped and we have to stay here
eight or ten years. The hair on our heads is getting
long again, and we begin to look like wild men of the
woods. One pocket comb does for the entire party;
two jack knives and a butcher knife. I have four keys
jingling away in my pocket to remind me of olden
times. Eli has a testament and Dave has a bible, and
the writer hereof has not. Still, I get scripture quoted
at all hours, which will, perhaps, make up in a
measure. Am at liberty to use either one of their
books, and I do read more or less. Considerable
travel on the highways, and going both ways as near
as we can judge. Dave wants to go out to the road
again but we discourage him in it, and he gives it up
for to-day at least. Are afraid he will get caught, and
then our main stay will be gone. Pitch pine knots
make a great smoke which rises among the trees
and we are a little afraid of the consequences; still,
rebels have plenty to do now without looking us up.
Many boats go up and down the river and can hear
them talk perhaps fifty rods away. Rebel paper that
Dave got spoke of Savannah being the point aimed
at by Sherman, also of his repulses; still I notice that
he keeps coming right along. Also quoted part of a
speech by Jefferson Davis, and he is criticised
unmercifully. Says nothing about any exchange of
prisoners, and our old comrades are no doubt
languishing in some prison. Later.—Considerable
firing up in vicinity of the bridge. Can hear volleys of
musketry, and an occasional boom of cannon.
Hurrah! It is now four o’clock by the sun and the
battle is certainly taking place. Later.—Go it Billy
Sherman, we are listening and wishing you the best
of success. Come right along and we will be with
you. Give ’em another—that was a good one. We
couldn’t be more excited if we were right in the midst
of it. Hurrah! It is now warm for the Johnnies. If we
had guns would go out and fight in their rear;
surround them, as it were. Troops going by to the
front, and are cavalry, should think, also artillery. Can
hear teamsters swearing away as they always do.
Later.—It is now long after dark and we have a good
fire. Fighting has partially subsided up the river, but
of course we don’t know whether Yankee troops
have crossed the river or not. Great deal of travel on
the road, but can hardly tell which way they are
going. Occasional firing. No sleep for us to-night. In
the morning shall go out to the road and see how
things look. Every little while when the battle raged
the loudest, all of us three would hurrah as if mad,
but we ain’t mad a bit; are tickled most to death.
 SAFE AND SOUND.

ONCE MORE SEE THE OLD FLAG AND THE BOYS IN BLUE—MR.
KIMBALL AND MRS. DICKINSON RECOMPENSED—FIND THE
NINTH MICHIGAN CAVALRY—INTERVIEWED BY GEN’L
KILPATRICK—ALL RIGHT AT LAST.

Dec. 23.—It is not yet daylight in the morning, and

are anxiously awaiting the hour to arrive when we
may go out to the road. Slept hardly any during the
night. More or less fighting all night, and could hear
an army go by toward Savannah, also some shouting
directly opposite us. Between the hours of about
twelve and three all was quiet, and then again more
travel. We conjecture that the rebel army has
retreated or been driven back, and that the Yankees
are now passing along following them up. Shall go
out about nine o’clock. Later.—Are eating breakfast
before starting out to liberty and safety. Must be very
careful now and make no mistake. If we run into a
rebel squad now, might get shot. We are nervous,
and so anxious can hardly eat. Will pick up what we
really need and start. Perhaps good bye, little house
on the banks of the Ogechee, we shall always
remember just how you look, and what a happy time
we have had on this little island. Dave says: “Pick up
your blanket and that skillet, and come along.” Night.
—Safe and sound among our own United States
Army troops, after an imprisonment of nearly
fourteen months. Will not attempt to describe my
feelings now. Could not do it. Staying with the 80th
Ohio Infantry, and are pretty well tired out from our
exertions of the day. At nine o’clock we started out
toward the main road. When near it Eli and I stopped,
and Dave went ahead to see who was passing. We
waited probably fifteen minutes, and then heard
Dave yell out: “Come on boys, all right! Hurry up!” Eli
and I had a stream to cross on a log. The stream was
some fifteen feet wide, and the log about two feet
through. I tried to walk that log and fell in my
excitement. Verily believe if the water had been a
foot deeper I would have drowned. Was up to my
arms, and I was so excited that I liked never to have
got out. Lost the axe, which Dave had handed to me,
and the old stand-by coverlid which had saved my
life time and again floated off down the stream, and I
went off without securing it—the more shame to me
for it. Dave ran out of the woods swinging his arms
and yelling like mad, and pretty soon Eli and myself
appeared, whooping and yelling. The 80th Ohio was
just going by, or a portion of it, however, and when
they saw first one and then another and then the
third coming toward them in rebel dress, with clubs
which they mistook for guns, they wheeled into line,
thinking, perhaps, that a whole regiment would
appear next. Dave finally explained by signs, and we
approached and satisfied them of our genuineness.
Said we were hard looking soldiers, but when we
came to tell them where we had been and all the
particulars, they did not wonder. Went right along
with them, and at noon had plenty to eat. Are the
guests of Co. I, 80th Ohio. At three the 80th had a
skirmish, we staying back a mile with some wagons,
and this afternoon rode in a wagon. Only came about
three or four miles to-day, and are near Kimball’s,
whom we shall call and see the first opportunity. The
soldiers all look well and feel well, and say the whole
confederacy is about cleaned out. Rebels fall back
without much fighting. Said there was not enough to
call it a fight at the bridge. Where we thought it a
battle, they thought it nothing worth speaking of.
Believe ten or so were killed, and some wounded.
Hear that some Michigan cavalry is with Kilpatrick off
on another road, but they do not know whether it is
the 9th Mich. Cav., or not. Say they see the cavalry
every day nearly, and I must keep watch for my
regiment. Soldiers forage on the plantations, and
have the best of food; chickens, ducks, sweet
potatoes, etc. The supply wagons carry nothing but
hard-tack, coffee, sugar and such things. Tell you,
coffee is a luxury, and makes one feel almost drunk.
Officers come to interview us every five minutes, and
we have talked ourselves most to death to-day. They
say we probably will not be called upon to do any
fighting during this war, as the thing is about settled.
They have heard of Andersonville, and from the
accounts of the place did not suppose that any lived
at all. New York papers had pictures in, of the scenes
there, and if such was the case it seems funny that
measures were not taken to get us away from there.
Many rebels are captured now, and we look at them
from a different stand point than a short time since.
Dec. 24.—This diary must soon come to an end.
Will fill the few remaining pages and then stop. Co.
“I” boys are very kind. They have reduced soldiering
to a science. All divided up into messes of from three
to five each. Any mess is glad to have us in with
them, and we pay them with accounts of our prison
life. Know they think half we tell them is lies. I regret
the most of anything, the loss of my blanket that
stood by me so well. It’s a singular fact that the first
day of my imprisonment it came into my possession,
and the very last day it took its departure, floating off
away from me after having performed its mission.
Should like to have taken it North to exhibit to my
friends. The infantry move only a few miles each day,
and I believe we stay here all day. Went and saw Mr.
Kimball. The officers commanding knew him for a
Union man, and none of his belongings were
troubled. In fact, he has anything he wants now.
Announces his intention of going with the army until
the war closes. Our good old friend Mrs. Dickinson
did not fare so well. The soldiers took everything she
had on the place fit to eat; all her cattle, pork,
potatoes, chickens, and left them entirely destitute.
We went and saw them, and will go to head-quarters
to see what can be done. Later.—We went to Gen.
Smith, commanding 3d Brigade, 2d Division, and told
him the particulars. He sent out foraging wagons,
and now she has potatoes, corn, bacon, cattle,
mules, and everything she wants. Also received pay
for burned fences and other damages. Now they are
smiling and happy and declare the Yankees to be as
good as she thought them bad this morning. The
men being under little restraint on this raid were often
destructive. Nearly every citizen declared their
loyalty, so no distinction is made. Gen. Smith is a
very kind man, and asked us a great many
questions. Says the 9th Michigan Cavalry is near us
and we may see them any hour. Gen. Haun also
takes quite an interest in us, and was equally
instrumental with Gen. Smith in seeing justice done
to our friends the Kimballs and Dickinsons. They
declare now that one of us must marry the daughter
of Mrs. Dickinson, the chaplain performing the
ceremony. Well, she is a good girl, and I should judge
would make a good wife, but presume she would
have something to say herself and will not pop the
question to her. They are very grateful, and only
afraid that after we all go away the rebel citizens and
soldiers will retaliate on them. Many officers have
read portions of my diary, and say such scenes as
we have passed through seem incredible. Many
inquire if we saw so and so of their friends who went
to Andersonville, but of course there were so many
there that we cannot remember them. This has been
comparatively a day of rest for this portion of the
Union army, after having successfully crossed the
river. We hear the cavalry is doing some fighting on
the right, in the direction of Fort McAllister. Evening.
—We marched about two or three miles and are
again encamped for the night, with pickets out for
miles around. Many refugees join the army prepared
to go along with them, among whom are a great
many negroes.
Dec. 25.—Christmas day and didn’t hang up my
stocking. No matter, it wouldn’t have held anything.
Last Christmas we spent on Belle Island, little
thinking long imprisonment awaiting us. Us escaped
men are to ride in a forage wagon. The army is
getting ready to move. Are now twenty-four miles
from Savannah and rebels falling back as we press
ahead. Night.—At about nine o’clock this morning as
we sat in the forage wagon top of some corn riding in
state, I saw some cavalry coming from the front.
Soon recognized Col. Acker at the head of the 9th
Michigan Cavalry. Jumped out of the wagon and
began dancing and yelling in the middle of the road
and in front of the troop. Col. Acker said: “Get out of
the road you —— lunatic!” Soon made myself known
and was like one arisen from the dead. Major
Brockway said: “Ransom, you want to start for home.
We don’t know you, you are dead. No such man as
Ransom on the rolls for ten months.” All remember
me and are rejoiced to see me back again. Lieut.
Col. Way, Surgeon, Adjutant, Sergeant-Major, all
shake hands with me. My company “A” was in the
rear of the column, and I stood by the road as they
moved along, hailing those I recognized. In every
case had to tell them who I was and then would go
up and shake hands with them at the risk of getting
stepped on by the horses. Pretty soon Co. “A”
appeared, and wasn’t they surprised to see me. The
whole company were raised in Jackson, Mich., my
home, and I had been regarded as dead for nearly a
year. Could hardly believe it was myself that
appeared to them. Every one trying to tell me the
news at home all at the same time—how I was
reported as having died in Richmond and funeral
sermon preached. How so and so had been shot and
killed, &c., &c. And then I had to tell them of who of
our regiment had died in Andersonville—Dr. Lewis,
Tom McGill and others. Although Jimmy Devers did
not belong to our regiment, many in our company
knew him, and I told them of his death. Should have
said that as soon as I got to the company, was given
Capt. Johnson’s lead horse to ride, without saddle or
bridle and nothing but a halter to hang on with. Not
being used to riding, in rebel dress—two or three
pails hanging to me—I made a spectacle for them all
to laugh at. It was a time of rejoicing. The Buck boys
did not get out of the wagon with me and so we
became separated without even a good bye. Before I
had been with the company half an hour Gen.
Kilpatrick and staff came riding by from the rear, and
says to Capt. Johnson: “Captain, I hear one of your
company has just joined you after escaping from the
enemy.” Capt. Johnson said, “Yes, sir,” and pointed
to me as a Sergeant in his company. General
Kilpatrick told me to follow him and started ahead at
a break neck pace. Inasmuch as the highway was
filled with troops, Gen. Kilpatrick and staff rode at the
side, through the fields, and any way they could get
over the ground. The horse I was on is a pacer and a
very hard riding animal and it was all I could do to
hang on. Horse would jump over logs and come
down an all fours ker-chug, and I kept hoping the
general would stop pretty soon; but he didn’t. Having
no saddle or anything to guide the brute, it was a
terrible hard ride for me, and time and again if I had
thought I could fall off without breaking my neck
should have done so. The soldiers all along the line
laughed and hooted at the spectacle and the staff
had great sport, which was anything but sport for me.
After a while and after riding five or six miles,
Kilpatrick drew up in a grove by the side of the road
and motioning me to him, asked me when I escaped,
etc. Soon saw I was too tired and out of breath. After
resting a few minutes I proceeded to tell him what I
knew of Savannah, the line of forts around the city,
and of other fortifications between us and the city, the
location of the rivers, force of rebels, etc. Asked a
great many questions and took down notes, or rather
the chief of staff, Estes by name, did. After an
extended conversation a dispatch was made up and
sent to Gen. Sherman who was a few miles away,
with the endorsement that an escaped prisoner had
given the information and it was reliable. General
Kilpatrick told me I would probably not be called upon
to do any more duty as I had done good service as a
prisoner of war. Said he would sign a furlough and
recommend that I go home as soon as
communication was opened. Thanked me for
information and dismissed me with congratulations
on my escape. Then I waited until our company, “A,”
came up and joined them, and here I am encamped
with the boys, who are engaged in getting supper.
We are only twelve or fourteen miles from Savannah
and the report in camp is to the effect that the city
has been evacuated with no fight at all. Fort
McAllister was taken to-day, which being the key to
Savannah, leaves that city unprotected, hence the
evacuation. Communication will now be opened with
the gunboats on the coast and I will be sent home to
Michigan. I mess with Capt. Johnson and there is
peace and plenty among us. I go around from mess
to mess this pleasant night talking with the boys,
learning and telling the news. O. B. Driscoll, Al.
Williams, Sergt. Smith, Mell Strickland, Sergt.
Fletcher, Teddy Fox, Lieut. Ingraham and all the rest
think of something new every few minutes, and I am
full. Poor Robt. Strickland, a boy whom I enlisted,
was shot since starting out on this march to the sea.
Others too, whom I left well are now no more. The
boys have had a long and tedious march, yet are all
in good health and have enjoyed the trip. They never
tire of telling about their fights and skirmishes, and
anecdotes concerning Kilpatrick, who is well liked by
all the soldiers. Am invited to eat with every mess in
the company, also at regimental head-quarters, in
fact, anywhere I am a mind to, can fill. And now this
Diary is finished and is full. Shall not write any more,
though I hardly know how I shall get along, without a
self-imposed task of some kind.

END OF DIARY.
 THE FINIS.

A BRIEF DESCRIPTION OF WHAT BECAME OF THE BOYS—

REFUSED PERMISSION TO GO HOME—A REFERENCE TO
CAPT. WIRTZ—RETURN HOME AT THE END OF THE WAR.

It may interest some one to know more of many

who have been mentioned at different times in this
book, and I will proceed to enlighten them.
George W. Hendryx came to the regiment in
March, 1865, when we were near Goldsboro, N. C.
He says that after running away from Andersonville
at the time of the discovery of a break in which all
intended to get away in the summer of 1864, he
traveled over one hundred and fifty miles and was
finally retaken by bushwhackers. He represented
himself as an officer of the 17th Michigan Infantry,
escaped from Columbia, S. C., and was sent to that
place and put with officers in the prison there,
changing his name so as not to be found out as
having escaped from Andersonville. In due time he
was exchanged with a batch of other officers and
went home North. After a short time he joined his
regiment and company for duty. He was both
delighted and surprised to see me, as he supposed
of course I had died in Andersonville, it having been
so reported to him at the North. He did valiant service
until the war was over, which soon happened. He
went home with the regiment and was mustered out
of service, since when I have never seen or heard of
him for a certainty. Think that he went to California.
Sergt. Wm. B. Rowe was exchanged in March,
1865, but never joined the regiment. His health was
ruined to a certain extent from his long confinement.
Is still alive, however, and resides at Dansville, Mich.
Sergt. Bullock was also exchanged at the same
time, but never did service thereafter. He is now an
inmate of a Michigan insane asylum, and has been
for some years, whether from the effects of prison life
I know not, but should presume it is due to his
sufferings there. His was a particularly sad case. He
was taken sick in the early days of Andersonville and
was sick all the time while in that place, a mere
walking and talking skeleton. There is no doubt in my
mind that his insanity resulted from his long
imprisonment.
E. P. Sanders arrived home in Michigan in April,
1865, and made me a visit at Jackson that Summer.
He was the only one of all my comrades in prison
that I came in contact with, who fully regained health,
or apparently was in good health. He was a
particularly strong and healthy man, and is now
engaged in farming near Lansing, Michigan.
Lieut. Wm. H. Robinson, who was removed from
Belle Isle, from our mess, it having been discovered
that he was an officer instead of an orderly sergeant,
was exchanged early in 1864, from Richmond, and
immediately joined his regiment, doing duty all the
time thereafter. Soon after my escape and while with
company “A,” a note was handed me from Capt.
Robinson, my old friend, he having been promoted to
a captaincy. The note informed me that he was only
a few miles away, and asked me to come and see
him that day. You may rest assured I was soon on
the road, and that day had the pleasure of taking my
dinner with him. He was on his general’s staff, and I
dined at head-quarters, much to my discomfiture, not
being up with such distinguished company. We had a
good visit, I remember, and I went to camp at night
well satisfied with my ride. Told me that a pipe which
I engraved and presented to him on Belle Isle was
still in his possession, and always should be. Was a
favorite with every one, and a fine looking officer. He
is now a resident of Sterling, Whiteside Co., Ill. Is a
banker, hardware dealer, one of the City Fathers, and
withal a prominent citizen. It was lucky he was an
officer and taken away from us on Belle Isle, for he
would undoubtedly have died at Andersonville, being
of rather a delicate frame and constitution.
My good old friend Battese, I regret to say, I have
never seen or heard of since he last visited me in the
Marine Hospital at Savannah. Have written many
letters and made many inquiries, but to no effect. He
was so reticent while with us in the prison, that we
did not learn enough of him to make inquiries since
then effective. Although for many months I was in his
immediate presence, he said nothing of where he
lived, his circumstances, or anything else. I only
know that his name was Battese, that he belonged to
a Minnesota regiment and was a noble fellow. I don’t
know of a man in the world I would rather see to-day
than him, and I hope some day when I have got rich
out of this book (if that time should ever come,) to go
to Minnesota and look him up. There are many
Andersonville survivors who must remember the tall
Indian, and certainly I shall, as long as life shall last.
Michael Hoare tells his own story farther along, in
answer to a letter written him for information
regarding his escape from the Savannah hospital.
Mike, at the close of the war re-enlisted in the regular
army and went to the extreme west to fight Indians,
and when his term of service expired again re-
enlisted and remained in the service. In 1878 he was