Bifunctional organic sponge photocatalyst for efficient cross-dehydrogenative coupling of tertiary amines to ketones

Article abstract of DOI:10.1039/c7cc06997a

A novel bifunctional organic sponge photocatalyst can enable the efficient coupling of tertiary amines with ketones in water. The asymmetric transformation can be also achieved by using this sponge photocatalyst.

Full text of DOI:10.1039/c7cc06997a

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Bifunctional organic sponge photocatalyst for efficient cross-
dehydrogenative coupling of tertiary amines to ketones
Teng Zhang, Weiwei Liang, Yuxing Huang, Xingrong Li, Yizhen Liu, Bo Yang, Chuanxin He, Xuechang
Zhou and Junmin Zhang*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
simultaneously anchoring a rose bengal (RB) dye photocatalyst[9]
A novel bifunctional organic sponge photocatalyst can provide
synergistic catalytic effects (visible-light photocatalysis and
enamine catalysis) and act as a hydrophobic microenvironment to
enable the efficient coupling of tertiary amines with ketones in
water. The asymmetric transformation can be also achieved by
using this bifunctional organic sponge photocatalyst.
and an enamine organocatalyst[10] onto a polydimethylsiloxane
(PDMS) sponge. This work has achieved not only the development
of new bifunctional photocatalysts but also the immobilization and
recycling of these catalysts. Furthermore, the PDMS sponge
provides a hydrophobic reaction microenvironment enabling the
efficient coupling of tertiary amines with ketones in water. In
addition, the asymmetric transformation can be also achieved by
using this bifunctional organic sponge photocatalyst.
Visible light-driven organic transformations are a very powerful and
efficient approach developed in response to topical interest in
renewable energy and green chemistry.[1] In the search for novel
transformations, cooperative photocatalysis has received
considerable attention in recent years,[2] as it has the potential to
enable unprecedented transformations that cannot proceed with
the photocatalyst alone. Most of the employed cooperative
photocatalysis systems rely on the use of two separate catalysts to
facilitate a single organic transformation.[3] A single bifunctional
photocatalyst able to simultaneously induce both photocatalysis
and another type of catalysis would be advantageous. In this area,
combining photocatalysts and transition-metal catalysts into one
complex to realize cooperative photoredox catalysis has been
developed considerably,[4] whereas combinations of a photocatalyst
with an organocatalyst[5] are much less widely reported. The first
successful example reported by Bach et al.[6] consisted of a chiral
hydrogen bonding-based thioxanthone that was used as both a
visible-light photocatalyst and an organocatalyst to promote an
intramolecular asymmetric [2+2] cycloaddition. Melchiorre et al.
also presented exquisite work using chiral enamine or iminium
intermediates as photocatalysts for effective asymmetric
transformations.[7] Despite these elegant pioneering studies,
bifunctional photocatalysts possessing the two functions of
visible-light catalysis and organocatalysis still require further
development. Continuing our recent interest on organic sponge
To obtain this bifunctional organic sponge photocatalyst, PDMS
was chosen as the sponge support because of its high transparency
and stability. The process of preparing the sponge catalyst is based
on the technology of polymer surface modification and classic
solid-phase peptide synthesis (SPPS).[11,12] As illustrated in Scheme 1,
after air plasma treatment to introduce the hydroxyl group, the
PDMS sponge was then functionalized with 3-aminopropyl
trimethoxysilane to convert the surface functional groups to amino
groups. Acting as a porous support material, the as-prepared amino
sponge (A-1) was then coupled with Fmoc-Glu(OtBu)-OH, leading to
the formation of a Glu-functionalized PDMS sponge (A-2). Next,
typical SPPS, including selective deprotection and amino acid
coupling (see the ESI for details), afforded
a bifunctional
photocatalyst supported by the PDMS sponge (A-7). The
morphology of the as-prepared sponge photocatalyst was
characterized by scanning electron microscopy (SEM, see ESI Fig.
S1), which showed that the PDMS sponge is a 3D-interconnected
porous material and is not destroyed by the surface modification
procedure. The corresponding SEM elemental mapping images
proved the homogenous distribution of Si, C, N, O, Cl and I elements
throughout the material. The catalyst loading on PDMS sponge, as
determined by elemental analysis, was 0.0176 mmol/g.
photocatalysis,[8] in this paper, we wish to report
a novel
To test the catalytic activity of the bifunctional PDMS sponge
photocatalyst, the cross-dehydrogenative coupling (CDC) reaction
between N-phenyltetrahydroisoquinoline and acetone was chosen
as a model reaction.[13,14] As shown in Table 1, various solvents were
screened to examine their effects on this reaction. Quite
interestingly, an excellent yield was obtained when the reaction
was carried out in water (Table 1, entry 12), whereas most of the
organic solvents afforded low yields of the product or even no
product. In this case, we propose that because of its inherent
bifunctional organic sponge photocatalyst, which was prepared by
a.College of Chemistry and Environmental Engineering, Shenzhen University,
Shenzhen, 518060, P. R. China
* E-mail: zhangjm@szu.edu.cn
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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O
O
O
OH
O
O
H
Fmoc-Glu(OtBu)-OH
Silanization
Toluene, 2 h
N
NH2
O
RB
O
O
OH
OH
Si
NH2
O
O
O
O
N
Fmoc 10% Piperidine
DMF, 30 min
N
Si
Si
HOBt, TBTU
DIEA, DMF, 5 h
H
H
HOBt, TBTU
DIEA, DMF, 5 h
PDMS-sponge
(after air plasma)
A-1
O
O
O
A-3
A-2
Cl
Cl
Cl
Cl
HO
I
O
O
O
RB
O
O
COOMe
NH
I
ONa
I
N
O
RB
NH
O
O
O
Si
N
H
O
O
N
Si
Boc
NH
O
H
0.2M HCl
80 oC, 5 h
O
O
N
Si
1) 0.2M HCl, 80 oC, 3 h
EDC HCl, DMAP
DMF, 5 h
H
A-6
O
I
2) 2% NaHCO3
O
O
O
OH
O
O
A-5
A-4
HN
A-7
COOMe
Scheme 1. Preparation of bifunctional organic sponge photocatalyst A-7 by a solid-phase synthetic strategy.
Table 1. Optimization of reaction conditions. [a] Table 2. Substrate scope of tertiary amines and ketones. [a]
Entry
x
Solvent
Yield (%) [b]
1
2
2
2
THF
trace
Toluene
trace
3
2
DCM
trace
4
2
EA
9
5
2
Dioxane
6
6
2
EtOH
15
7
2
NMP
trace
8
2
DMF
18
9
2
ACN
12
10
11
12
13
14
2
DMSO
trace
2
2-methyl-2-pentanol
30 [c]
2
H2O
H2O
H2O
81
72
1.5
3
95 (93 [d], 36[e], 11 [f]
)
[a] Reactions were performed using 1a (0.1 mmol) and 2a (1.0 mmol) in
2 mL of solvent and were catalyzed by sponge catalyst A-7 at room
temperature with a 12 W green LED light for 24 hours. [b] Yield was
determined by 1H NMR with 1,3,5-trimethoxybenzene as an internal
standard. [c] < 2% ee, determined by chiral HPLC analysis on an AS-H
column. [d] Isolated yield; 7.4% ee. [e] In the absence of LED
irradiation. [f] In the dark.
[a] Reactions were performed using 1a-n (0.5 mmol) and 2a-i (5.0
mmol) in 5 mL of H2O and were catalyzed by 3 mol% sponge catalyst
A-7 with 12 W green LED light.
donating substituents on the N-phenyl ring (Table 2, 3a-j).
Conversely, the substrates with electron- withdrawing groups
required longer reaction times to go to completion and provide
satisfactory yields (Table 2, 3h and 3j). Initially, only low yields were
obtained for the substrates bearing a methoxyl group on the aryl
ring of the tetrahydroisoquinoline at room temperature. Under
slightly modified conditions (50 °C for 24 hours), however, products
3k-m were obtained with improved yields. In addition, a simple
tertiary amine also provided the corresponding product (Table 2,
3n).
hydrophobic nature,[15] the PDMS sponge might provide
hydrophobic reaction microenvironment to enable the efficient
a
coupling in water. In addition, the control experiments also showed
that proline moiety on the catalyst (A-7) could greatly accelerate
the CDC reaction (see ESI Table S1), however, it is not an ideal
enamine catalyst for effective asymmetric transformations due to
its methyl esterification (Table 1, entries 11 and 14). The green LED
light is essential for the reaction as low conversion was observed
when the reaction was conducted either in the normal light or dark
(Table 1, entry 14). To our delight, the best result was achieved with
3 mol% sponge photocatalyst, and the corresponding isolated yield
was 93% (Table 1, entry 13).
Further investigation was conducted using 1a to screen various
ketones for their suitability for cooperative sponge photocatalysis.
Generally, methyl ketones performed quite well at room
temperature and furnished the corresponding products with high
yields (Table 2, 3o-q). Bulky methyl ketones also gave good results
when the reaction time was prolonged (Table 2, 3r-t). Diketone
compounds, such as acetylacetone, can be transformed into the
corresponding β-amino product smoothly (Table 2, 3u). Notably,
3-pentanone can also be coupled with 1a in water-bath for 24 hours
to give the corresponding product in moderate yield (Table 2, 3v).
Under optimal conditions, the substrate scope of the
cooperative sponge photocatalysis was investigated. Generally,
N-phenyltetra-hydroisoquinoline
substrates
with
various
substituents afforded the product in good yields. Particularly
excellent yields were noted for the substrates with electron-
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With the success of the bifunctional sponge photocatalyst in
intermolecular CDC reactions, the standard conditions were then
directly applied to an intramolecular CDC reaction to deliver
ring-fused tetrahydroquinolines. The synthesis of such compounds
using a greener protocol is highly desirable because of their
potential biological effects.[16] As shown in Table 3, this
methodology could be applied to intramolecular CDC reactions to
furnish the corresponding ring-fused tetrahydroquinoline
derivatives (5a-d) in satisfying yields.
Scheme 2. Preparation of bifunctional organic sponge photocatalyst A-8.
To investigate the recovery and recycling of the bifunctional
sponge photocatalyst, the model reaction between 1a and 2a was
chosen for further investigation. In general, simply removing the
sponge and washing it with alcohol allowed the convenient
separation and reuse of the photocatalyst; no significant loss of
catalytic activity was observed after at least ten cycles. Importantly,
the yields were slightly decreased after 7 reuse cycles at room
temperature. Fortunately, the catalytic activity was efficiently
recovered when the reaction temperature was increased to 50 °C.
Ultimately, 87% yield could be achieved after 10 cycles (see the ESI
for details).
Table 4. Preliminary study on asymmetric CDC reaction by bifunctional
organic sponge photocatalyst.[a]
The possible application of this novel bifunctional PDMS sponge
catalyst in industry was demonstrated using an easy-to-build
[a] Reactions were performed using 1a (0.5 mmol) and 2j-m (5.0
mmol) in 3 mL 2-methyl-2-pentanol and were catalyzed by 3 mol%
sponge photocatalyst A-8 at room temperature with 12 W green LED
light. The diastereomeric ratio, anti/syn, was determined by 1HNMR
analysis. The enantiomeric excess was determined by chiral HPLC
analysis. [b] 21% yield, 7:1 d.r., 64% ee, in the absence of LED
irradiation. [c] Trace, in the dark.
circulating flow reactor, as described in our previous work.[8]
A
gram-scale reaction of the N-phenyltetrahydro- isoquinoline and
acetone model system was tested, and 91% isolated yield was
achieved after 36 hours (see the ESI for details).
In order to achieve asymmetric CDC coupling of tertiary amines
with ketones, another chiral bifunctional sponge photocatalyst (A-8)
was further prepared by replacing L-proline methyl ester moiety of
A-7 with L-proline sodium salt (Scheme 2). By using A-8 as the
catalyst, the asymmetric CDC reactions between 1a and
cycloketones were investigated.[14d,k,l] Under optimized conditions
(see ESI Table S2), the reaction proceeded smoothly and the desired
products (Table 4, 3w-z) were obtained with moderate yields
(60–77%), good to excellent diastereo- and enantioselectivities (up
to 15 : 1 d.r. and 81.6% ee). The enantioselectivity control pathway
of sponge catalyst is believed to be consistent with the mechanism
of chiral organic contact ion pairs, as proposed by Wang et al.[14d]
This preliminary result of asymmetric transformation indicates that
the strategy of chiral bifunctional organic sponge photocatalysis
would be a promising and greener approach for asymmetric organic
transformations.
catalyze the CDC of tertiary amines with ketones in water under
visible-light irradiation. Preliminary study showed that this novel
binfunctional organic sponge photocatalyst can also catalyze
asymmetric transformation with good enantioselectivities. This
strategy shows promise for achieving other, more challenging
photocatalytic processes because of its advantages of facile catalyst
preparation, environmental friendliness, convenient separation,
and easy catalyst recycling and workup. Efforts toward the
expansion of this strategy to other types of bifunctional organic
sponge photocatalysts and its application in asymmetric organic
transformations are currently ongoing in our laboratories.
We are grateful to the National Natural Science Foundation of
China (21402124, 21404072 and 21605104), the Training
Foundation for Outstanding Young Teachers of Guangdong
(YQ2015145), the Shenzhen Science and Technology Foundation
(JCYJ20150324141711702, JCYJ20170302143658923, JCYJ20150324
140036849 and JCYJ20140418182819116), and the Natural Science
Foundation of SZU (827000038).
In conclusion, we have successfully developed
a novel
bifunctional organic sponge photocatalyst that can efficiently
Table 3. Substrate scope of intramolecular CDC reaction. [a]
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[a] Reactions were performed using 4a-d (0.5 mmol) in 5 mL of H2O and
were catalyzed by 3 mol% sponge catalyst A-7 at room temperature
with 12 W green LED light. [b] 17% yield, in the absence of LED
irradiation. [c] Trace, in the dark.
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2 For reviews on cooperative photoredox catalysis, see: a) M. N.
ARTICLE
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5
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1669-1730.
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ChemComm
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DOI: 10.1039/C7CC06997A
Journal Name
COMMUNICATION
Table of Contents
A novel bifunctional organic sponge photocatalyst can provide synergistic catalytic effects (visible-light photocatalysis
and enamine catalysis) and act as a hydrophobic microenvironment to enable the efficient coupling of tertiary amines
with ketones in water. The asymmetric transformation can be also achieved by using this sponge photocatalyst.
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