Non-Heme-Type Ruthenium Catalyzed Chemo- and Site-Selective C?H Oxidation

Article abstract of DOI:10.1002/asia.202000134

Herein, we developed a Ru(II)(BPGA) complex that could be used to catalyze chemo- and site-selective C?H oxidation. The described ruthenium complex was designed by replacing one pyridyl group on tris(2-pyridylmethyl)amine with an electron-donating amide ligand that was critical for promoting this type of reaction. More importantly, higher reactivities and better chemo-, and site-selectivities were observed for reactions using the cis-ruthenium complex rather than the trans-one. This reaction could be used to convert sterically less hindered methyne and/or methylene C?H bonds of a various organic substrates, including natural products, into valuable alcohol or ketone products.

Full text of DOI:10.1002/asia.202000134

CHEMISTRY
AN ASIAN JOURNAL
www.chemasianj.org
Accepted Article
Title: Non-Heme-Type Ruthenium Catalyzed Chemo- and Site-
Selective C–H Oxidation
Authors: Daiki Doiuchi, Tatsuya Nakamura, Hiroki Hayashi, and
Tatsuya Uchida
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10.1002/asia.202000134
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Non-Heme-Type Ruthenium Catalyzed Chemo- and Site-Selective
C–H Oxidation
Daiki Doiuchi,[b] Tatsuya Nakamura,[b] Hiroki Hayashi[a] and Tatsuya Uchida*[a,c]
Dedication to 100th Annual Meeting of the CSJ
[a]
Prof. Dr. T. Uchida: 0000-0002-6511-5752, Dr. H. Hayashi: 0000-0003-2081-6886
Faculty of Arts and Science
Kyushu University
744, Motooka, Nishi-ku, Fukuoka, 819-0395, Japan
E-mail: uchida.tatsuya.045@m.kyushu-u.ac.jp
D. Doiuchi, T, Nakamura
Department of Chemistry, Graduate School of Science
Kyushu University
[b]
[c]
744, Motooka, Nishi-ku, Fukuoka, 819-0395, Japan
Prof. Dr. T. Uchida
International Institute for Carbon-Neutral Energy Research (WPI-I2CNER)
Kyushu University
744, Motooka, Nishi-ku, Fukuoka, 819-0395, Japan
Supporting information for this article is given via a link at the end of the document.
Abstract: Herein, we developed a Ru(II)(BPGA) complex that could
be used to catalyze chemo- and site-selective C–H oxidation. The
described ruthenium complex was designed by replacing one pyridyl
group on tris(2-pyridylmethyl)amine with an electron-donating amide
ligand that was critical for promoting this type of reaction. More
importantly, higher reactivities and better chemo-, and site-
selectivities were observed for reactions using the cis-ruthenium
complex rather than the trans-one. This reaction could be used to
convert sterically less hindered methyne and/or methylene C–H
bonds of a various organic substrates, including natural products, into
valuable alcohol or ketone products.
manganese complexes to effect change have been developed.[4,8]
However, these reactions often suffer from catalyst degradation
via oxidative decomposition or dimerization, necessitating the use
of a high catalyst load in order to accomplish results.[9] An
alternative method for achieving high reactivity, selectivity, and
catalytic durability for C–H bond oxidations is sorely needed. As
such, various types of catalytic methods, structures, and the
electronic nature of non-heme enzymes have become attractive
targets for research and development in this field. Moreover,
biomimetic oxidation mechanisms, hydrogen atom transfer (HAT)
reactivity of metal(oxo) intermediates, and putative reactive
species in a reaction are all enhanced by the presence of better
electron-donating axial ligands on the catalyst.[10] Typical non-
heme model catalysts have an electron-donating nitrogen atom at
the apical site and are thus expected to improve HAT reactivity.
Major advancements have been made in the development of iron
or manganese catalysts in this field,[6-8] and ruthenium
complexes[11,12] have also attracted much attention owing to their
extensive redox and coordination chemistry. Thus, we were
intrigued by the use of non-heme-type ruthenium complexes as
catalysts for C–H oxidation. In this study, we found that the newly
Since C–H bonds are the stable and ubiquitous backbones of
every organic molecule, their functionalization via chemo- and
site-selective methods has been the focus of research interest.
C–H bond functionalization is an extremely powerful and useful
tool in organic synthesis because C–H bond oxidation reactions
offer a step-economic strategy for the construction of organic
molecules.[1,2] It is well known that various enzymes, such as iron-
containing heme- and non-heme proteins, are capable of
catalyzing C–H oxidation reactions with almost complete chemo-
and site selectivity (Scheme 1, a).[3-8] As a result, various bio-
inspired catalysts have been developed (Scheme 1, b), in
particular, metalloporphyrins, which are typical heme oxygenase
enzymes; one such well-documented example is the cytochrome
P450 family of enzymes.[3,5] Non-heme enzymes, such as
methane monooxygenase and α-ketoglutarate-dependent
oxygenase, are also known to activate aliphatic C–H bonds.[4,6-8]
Que and coworkers reported using a non-heme model complex,
namely, (µ-oxo)diferric(TPA) [TPA: tris(2-pyridylmethyl)amine], to
catalyze alkane C–H oxidation.[6] As a remarkable demonstration
of artificial non-heme-type catalysts, iron-PDP [PDP: N,N′-bis(2-
pyridylmethyl)-2,2′-bipyrrolidine] complexes were shown to
exhibit superb site selectivity during the C–H hydroxylation of
complex molecules and natural products.[7] Since the publication
of this pioneering report, numerous methods utilizing iron and
designed
ruthenium(II)[bis(2-pyridylmethyl)glycinamide]
[Ru(II)(BPGA)] complex exhibited excellent catalytic activity and
site selectivity (Scheme 1, c).
1
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a) Typical active core structure of heme and non-heme enzymes
H
H
Cl
N
N
His
His
OH2
His
His
N
N
N
OH2
FeII
N
N
FeII
H2N
N
S
N
N
Cl
N
N
II
N
N
Fe
HN
HOOC
O
HN
N
N
COO
N
Ru
P
Ru
H
O
Asp
HN
N
P
O
HOOC
N
His
O
Heme
cytochrome P450
Non-heme
Rieske Dioxygenase
Cysteine Dioxygenase
Cl
b) Typical bio-inspired transition metal catalysts
”R
N
Cl
R
R”
R
N
N
M
M
N
N
N
’R
O
O
R
trans-1b
Figure 1. ORTEP diagram of cis-1b and trans-1b.
cis-1b
R
R’
metalloporphyrin
metallosalen
N
FeII
N
N
N
N
N
II
FeII
NCCH
3
NCCH
3
NCCH
Fe
3
N
N
N
NCCH
NCCH
NCCH
3
3
3
N
N
N
The catalysis of Ru(II)(BPGA) 1a and Ru(II)(TPA) complexes
for the C–H oxidation of adamantane 2a as the model substrate
was conducted (Scheme 3). In this case, both trans- and cis-
Ru(II)(BPGA) 1a exhibited better catalytic activity than
Ru(II)(TPA), in particular, cis-1a, which produced 1-adamantanol
3a in much higher yields with excellent chemoselectivity and site
selectivity when compared with its trans-1a. Initial reaction
analysis indicated that C–H oxidation using trans- and cis-1a as
the catalyst experienced different reaction rates. There was no
interconversion between trans-1a and cis-1a during C–H
oxidation; this indicated that the ruthenium(oxo) derivatives from
the cis-isomer and iodosylbenzene (PhI=O), which acted as the
terminal oxidant, were the primary active species in this reaction
(Figure 2).[11c]
(SbF6)2
(ClO4)2
(SbF6)2
[Fe(II)(TPA)](ClO4)
c) This works
[Fe(II)(BPMCN)](SbF6)
[Fe(II)(PDP)](SbF6)
H
H
Cl
N
N
R
N
R
N
II
N
O
PPh3
II
Ru
N
O
PPh3
Ru
Cl
N
N
Cl
Cl
1a: R = Ph
Ru(II)(BPGA) cis-1 1b: R = 2,6-Me2C6H3
Ru(II)(BPGA) trans-1
higher catalytic reactivity, chemo- and site-selectivity, broader scope
Scheme 1. Bio-inspired transition metal catalyst.
To prepare the ruthenium complexes, a series of BPGA
ligands
was
synthesized
from
2-chloromethylpyridine
OH
hydrochloride, glycine methyl ester hydrochloride, and various
anilines in three steps: 1) N,N-2-pyridylmethylation,[13] 2)
hydrolysis of the ester, and 3) a dehydrating condensation
(Scheme 2). Then, trans- and cis-Ru(II)(BPGA) complexes 1 were
obtained via the simple treatment of the ligand with RuCl2(PPh3)3
in ethanol under reflux conditions. Single-crystal X-ray analysis of
the trans- and cis-Ru(II)(BPGA) complexes of 1 clearly revealed
that the two nitrogen atoms of the pyridine units were in cis or
trans-positions relative to each other (Figure 1). The resulting
trans- and cis-1a complexes exhibited the ability to reversibly
couple reaction with Ru(II)/Ru(III) in 0.24 and 0.27 V versus
Fc/Fc+ in CH2Cl2, respectively.[14]
Ru cat. (2 mol%)
PhI=O (1.5 equiv.)
OH
O
H
+
+
+
OH
OH
H
(CHCl2)2, 30 °C
12 h
2a
3a
4a
5a
6a
[Ru(TPA)(PPh3)Cl]Cl; 3a: 11%, 4a: 0%, 5a: 0%, 6a: 0.4%, 3˚/2˚ = 24/1
trans-1a; 3a: 26%, 4a: 0.4%, 5a: 0.4%, 6a: 1.1%, 3˚/2˚ = 25/1
cis-1a; 3a: 53%, 4a: 2.1%, 5a: 0%, 6a: 1.4%, 3˚/2˚ = 42/1
Scheme 3. Preliminary studies ruthenium-catalyzed C–H oxidation. Reactions
were conducted with 2a (0.1 mmol), Ru-cat. (2.0 µmol), and PhI=O (0.15 mmol,
1.5 equiv.) in (CHCl2)2 (0.2 M) at 30 °C for 12 h.
trans- or cis-1a (2 mol%)
PhI=O (1.5 equiv.)
+
+
+
5a
6a
2a
3a
4a
(CHCl2)2, 30 °C
90
80
70
60
50
40
30
20
10
0
0.0
H3CO
N
KI (1.0 eq.)
K2CO3 (10 eq.)
O
N
LiOH•H2O
(1.2 eq.)
H3CO
O
Cl
R² = 0.920
+
-0.4
-0.8
-1.2
-1.6
-2.0
N
•HCl
MeCN,
reflux, over night
H2O/MeCN (1:1)
rt, 4 h
NH2•HCl
N
(2.5 eq.)
R² = 0.992
HO
N
H
O
N
O
N
H2N–R (1.1 eq.)
DMT-MM (1.5 eq.)
R
RuCl2(PPh3)3
(1.1 eq.)
N
Ru(BPGA) 1
N
iPrOH, rt, over night
0
10
20
30
time (h)
40
50
0
10
20
time (h)
30
40
50
N
EtOH
reflux, 4 h
N
Figure 2. Monitoring trans-1a and cis-1a-catalyzed C–H hydroxylation of
adamantane 2a.
Scheme 2. Preparation of Ru(II)(BPGA) complexes 1.
Based on these results, the optimization of C–H oxidation of
adamantane 2a was conducted (Table 1). Initial examination of
the catalyst revealed that the ruthenium complex cis-1b bearing
2,6-dimethylaniline unit exhibited slightly higher reactivity than all
the other ruthenium complexes (entry 1).[14] Moreover, the
2
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10.1002/asia.202000134
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addition of trifluoroacetic acid (TFA) enhanced reaction rate
without the diminishing chemo- and site-selectivities (entry 2).
Although the exact mechanistic details of how the addition of acid
affects the reaction are unclear at present, it is theorized that the
acids disassemble the relatively less-soluble oligomeric PhI=O to
generate a soluble monomer,[15] and enhance the reactivity of the
putative ruthenium(oxo) species.[16] Increasing the amount of TFA
in the reaction dramatically improved the desired C–H
hydroxylation process (entries 3-5).
afforded to the corresponding ketone products 3p–t in good to
high yields. Under the catalytic conditions, (–)-ambroxide 2u
obtained (+)-sclareolide 3u as a sole product even on 1.0 mmol
scale. β-Estradiol diacetate 2v could be oxidized benzylic
methyne and methylene C–H and gave 9-hydroxy-6-keto b-
estradiol derivatives as the major product.[17]
cis-1b (2 mol%)
PhI=O (1.5–4 equiv.)
TFA (50 mol%)
H
OH
R2
O
or
R2
R3
Table 1. Investigation of Ru(II)(BPGA) cis-1b-catalyzed C–H hydroxylation of
adamantane 2a.[a]
R1
R1
R3
(CHCl2)2, 35 °C
R1 R2
2
3
27% conv. (24 h)[a,b,c]
86% conv., 60% yield,
(C7/C3/C3,7 = 24/1/4, 24 h)[a]
entry
Ru-cat.
cis-1b
cis-1b
cis-1b
cis-1b
cis-1b
additive
3a / 4a / 5a /6a (%)[b]
59 / 2.9 / 0 / 1.5
46 / 1.7 / 0 / 1.1
61 / 4.6 / 0 / 1.7
71 / 12 / 0 / 2.2
3°/2°[c]
43/1
44/1
41/1
43/1
43/1
TFA 3 equiv.:
TFA 0.5 equiv.:
HO
OAc
7
3
1[d]
2
–
3b
HO
HO
HO
OBz
OBz
CF3CO2H (0.25 equiv.)
CF3CO2H (0.50 equiv.)
CF3CO2H (1.0 equiv.)
CF3CO2H (3.0 equiv.)
OBz
3c
3d
3e
68% yield (36 h)
77% yield (30 h)
62% yield (24 h)
3
OH
OH
4
HO
OH
OBz
5
77 / 8.4 / 0.6 / 1.6
H
3g
3h
3f
77% yield (30 h)
34% yield (24 h)
58% yield (3 h)
[a] Reaction were run with 2a (0.1 mmol), cis-1b (2.0 µmol), and PhI=O (0.15
mmol, 1.5 equiv.) in (CHCl2)2 (0.2 M) at 30 °C for 1 h, unless otherwise noted.
[b] Yields were determined by GC Analysis. [c] Regioselectivities were
determined as follows; 3°/2° = 3a(%) + 2x4a(%) / 5a(%) + 6a(%). [d] Run for
12h.
CO2Me
HO
OH
OAc
H
3
OH
HO
H
3i
3j
H
H
77% yield[a] (6 h)
53% yield (18 h)
3k
56% yield (48 h)
We conducted further the C–H oxidation of various
substrates using cis-1b as the catalyst with PhI=O as the terminal
oxidant (Scheme 4). The reaction of (±)-dihydrocitronellol acetate
2b with 3.0 equiv. of TFA and 1.5 equiv. of PhI=O at 30 ˚C gave
the 7-hydroxy compound 3b as the major product in a good site-
selective manner in 27% conversion. Fortunately, the chemical
yield of 3b could be improved to 60% in a C7/C3/C3,7 = 24/1/4 by
the loading 0.5 equiv. of TFA and using 2.5 equiv. of PhI=O at 35
˚C. Under these conditions, various carbohydrates could be
oxidized at the sterically less-hindered 3˚ C–H bonds to hydroxy
group with excellent site-selectivities. From alkylbenzoate
derivatives (2c-2f), the corresponding tert-alcohols (3c-f) could be
obtained with acceptable yields, respectively. The sterically less-
hindered 2c-e exhibited better reactivity than its counterpart 2f.
Cyclic substrate such as cis-decalin 2g was underwent
stereospecific 3˚ selective C–H oxidation. The reactions of tert-
alcohols (2h and 2i) also contained methyne C–H bonds and
underwent transformation. Moreover, complex 1b-catalyzed C–H
oxidations could be applied to late-stage functionalization of
highly complicated natural products. Cedrol 2j could be oxidized
at the C3 position in 53% yield, whereas the hydroxylation of the
deoxycholic acid derivative 2k was proceeded at the C5 in 56%
yield. This type of C–H oxidation also converted benzylic methyne
and methylene C–H bonds to their corresponding trat-alcohols
and ketones. Cumene derivatives (2l and 2m) could be obtained
the corresponding tert-alcohols in good yields. The catalytic C–H
bond oxidation can convert methylene C–H bonds to the
AcO
5 OH
O
3l (R = COMe)
57% yield (18 h)
OH
3m (R = NO2)
54% yield (30 h)
3p-t
R
R
R = Cl (3p)[a,e]: 72% yield (6h)
82% yield (12h)
O
O
Br (3q)[a,e]: 77% yield (6 h)
84% yield (12h)
NO2 (3r)[a,e]: 35% yield (24 h)
Me (3s)[a,e]: 67% yield (6 h)
H (3t)[a,e]: 55% yield (6 h)
3n[a,d]
3o[a,d]
75% yield (2 h)
96% yield (2 h)
O
12
OAc
O
HO
H
3u[f]
H
9
3v[b,e,h]
H
95% yield (95%)[f,g]
AcO
46% yield(48 h)
H
(1.5 h)
6
O
Scheme 4. Substrate scope of cis-1b-catalyzed C–H oxidation. Reactions were
conducted with 2 (0.2 mmol), cis-1b (2 mol%), TFA (0.5 equiv.) and PhI=O (2.5
equiv.) in (CHCl2)2 (0.4 M) at 35 °C for 1.5-48 h, unless otherwise noted. [a]
Determined by GC analysis. [b] Run on a 0.1 mmol scale. [c] Run with PhI=O
(1.5 equiv.) in (CHCl2)2 (0.2 M) at 30 °C. [d] Run with PhI=O (2.0 equiv.). [e] Run
with PhI=O (4.0 equiv.). [f] Run with PhI=O (3.0 equiv.). [g] Run on 1.0 mmol
scale. [h] Run without TFA in (CHCl2)2 (0.2 M).
We investigated the oxidation of cyclobutanol in order to
gain mechanistic insight into the route to the present C–H
hydroxylation. Under oxidation conditions, cyclobutanone was
formed as the major product, and no ring opening products were
observed.[18] This observation indicated that Ru(II)(BPGA) cis-1b-
catalyzed C–H oxidation was underwent via hydrogen atom
transfer with a two-electron oxidation process.[18c]
corresponding
ketones.
Indan
2n
and
1,2,3,4-
tetrahydronaphthalene 2o were also compatible with the reaction
conditions and could be converted to 1-indanone 3n and 1-
tetralone 3o in a chemoselective manner, respectively. Under cis-
1b-catalyzed oxidation, overoxidation products such as
hydroxyketones and diketones were observed in only trace
amounts. A series of ethyl benzene derivatives 2p–t could be
In summary, a durable non-heme Ru(II)(BPGA) cis-1b was
constructed with the aim of achieving high methyne C–H bond
selective oxidation via the addition of TFA. Ru(II)(BPGA) complex
3
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less-hindered tertiary C–H bond with high chemoselectivity.
Notably, late-stage C–H oxidation of highly complicated
molecules also proceeded in a highly chemo- and site-selective
manner. Based on the mechanistic studies, cis-1b catalyzed the
two-electron oxidation of the C–H bonds. Although further insight
into the mechanism must be obtained through additional kinetic
and control studies, the present research has opened a new way
toward the step-economic synthesis of alcohols.
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Acknowledgements
Financial Support from JSPS KAKENHI Grant Number 18H04264 in
Precisely Designed Catalysis with Customized Scaffolding; The
International Institute for Carbon- Neutral Energy Research (WPI-I2CNER)
from MEXT, Japan, are grateful acknowledged.
Keywords: C–H oxidation• Non-Heme model • Hydroxylation•
Ruthenium • Site-selective oxidation
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4
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10.1002/asia.202000134
Chemistry - An Asian Journal
COMMUNICATION
Entry for the Table of Contents
H
Cl
N
cis-Ru(II)(BPGA)
N
II
O
Ru
N
H
OH
R2
PhI=O
PPh3
N
R2
R3
R1
R1
R3
high site-selective catalytic C–H oxidation
Cl–
cis-Ru(II)(BPGA)
Non-heme ruthenium catalysis for selective C–H oxidation is described. The newly designed cis-Ru(BPGA) complex bearing a
glycinamide unit promotes oxidation of methyne and methylene C–H bonds selectively with iodosylbenzene as the terminal oxidant.
The catalytic system can be applied for a wide range of organic molecules including natural products to provide valuable alcohols or
ketones with high chemo- and site-selectivity.
5
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