Visible Light Induced Bifunctional Rhodium Catalysis for Decarbonylative Coupling of Imides with Alkynes

Article abstract of DOI:10.1002/anie.202010782

Transition metal catalyzed decarbonylation offers a distinct synthetic strategy for new chemical bond formation. However, the π-backbonding between CO π* orbitals and metal center d-orbitals impedes ligand dissociation to regenerate the catalyst under mild reaction conditions. Developed here is visible light induced rhodium catalysis for decarbonylative coupling of imides with alkynes under ambient conditions. Initial mechanistic studies suggest that the rhodium complex simultaneously serves as the catalytic center and photosensitizer for decarbonylation. This visible light promoted catalytic decarbonylation strategy offers new opportunities for reviewing old transformations with ligand dissociation as a rate-determining step.

Full text of DOI:10.1002/anie.202010782

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Visible Light-Induced Bifunctional Rhodium Catalysis for
Decarbonylative Coupling of Imides with Alkynes
Authors: Xiang-Ting Min, Ding-Wei Ji, Yu-Qing Guan, Shi-Yu Guo,
Yan-Cheng Hu, Boshun Wan, and Qing-An Chen
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202010782
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Visible Light-Induced Bifunctional Rhodium Catalysis for
Decarbonylative Coupling of Imides with Alkynes
Xiang-Ting Min, Ding-Wei Ji, Yu-Qing Guan, Shi-Yu Guo, Yan-Cheng Hu, Boshun Wan, Qing-An
Chen*
[a]
X. T. Min, D. W. Ji, Y. Q. Guan, S. Y. Guo, Dr. Y. C. Hu, Prof. Dr. B. Wan, Prof. Dr. Q. A. Chen.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
457 Zhongshan Road, Dalian 116023, China
E-mail: qachen@dicp.ac.cn, Homepage: http://www.lbcs.dicp.ac.cn
X. T. Min, D. W. Ji.
[b]
University of Chinese Academy of Sciences
Beijing 100049, China
Supporting information for this article is given via a link at the end of the document.
Abstract: Transition metal-catalyzed decarbonylation offers
a
distinct synthetic strategy for new chemical bond formation. However,
the π-backbonding between CO π* orbitals and metal center d-
orbitals impedes ligand dissociation to regenerate catalyst under
mild condition. Herein, we developed a visible light-induced rhodium
catalysis for decarbonylative coupling of imides with alkynes under
ambient conditions. Initial mechanistic studies suggest that the
rhodium complex simultaneously serves as the catalytic center and
photosensitizer for decarbonylation. This visible light-promoted
catalytic decarbonylation strategy offers new opportunities for
reviewing old transformations with ligand dissociation as a rate
determining step.
Well known ligand dissociation is a common and important step
in transition metal catalysis.[1] This fundamental step spares
vacant coordination sites and simultaneously affects the steric
and electronic properties on the metal center.[2] Dissociation of
the product or by-product usually either regenerates the starting
catalyst or generates a species that will be converted to the
starting catalyst. Conversely, transition metal reagent must be
used in stoichiometric quantities instead of a catalyst.[3] For
example, Tsuji and Ohno reported the famous Tsuji-Wilkinson
decarbonylation reaction of the aldehydes with stoichiometric
amounts Wilkinson’s complex RhCl(PPh3)3 (Scheme 1a).[4] As
one of the most strongly π-accepting ligand, carbon monoxide
(CO), the π-backbonding between CO and Rh impedes the
ligand dissociation step to regenerate Wilkinson’s catalyst under
mild condition.[5] Through a compromise approach, scientists
have taken advantage of thermal dissociation (usually 110-
200 °C)[6] of CO from resting state of catalyst to facilitate the
catalytic decarbonylation using various transition metals (Rh,[7]
Pd, [8] Ni, [9] Ru, [10] Pt,[11] Ir[12] etc. [6]) (Scheme 1b). Therefore, it is
of great interest to develop mild methods for the catalytic
decarbonylation. [6]
Scheme 1. Transition metal-catalyzed decarbonylation.
Scheme 2. Initial investigation on thermal- or photo-induced Rh-catalyzed
decarbonylative coupling.
As an alternative approach, photochemically induced ligand
To verify our proposal, we chose decarbonylative coupling of
imides with alkynes as model reaction (Scheme 2). Matsubara
and our group have previously demonstrated that this
transformation could be realized under Ni[16] or Co[17] catalysis
dissociation has been employed for the simple metal carbonyl
complexes Cr(CO)6,[13] Fe(CO)5,[13] and Ni(CO)4
etc. under
[13]
ultraviolet light irradiation. Inspired by these stoichiometric
precedents in combination with growing field of photo-induced
o
(10–20 mol%) via a thermally induced approach (110–130 C).
catalysis,[14,15] we
envisioned
developing
a
catalytic
Given the unique property of Rh on decarbonylation reactions,[7,
decarbonylation promoted by photochemically induced CO
dissociation using visible light. Herein, we demonstrated a
visible light-driven bifunctional rhodium catalysis for
decarbonylative coupling of imides with alkynes under mild
condition (Scheme 1c).
15g]
we were curious about its performance on decarbonylative
coupling of imides with alkynes. An initial investigation
suggested the functional group on the nitrogen atom of imide 1
plays an important role on reaction outcomes (Scheme 2).
Under thermally induced conditions (150 oC), low yields (11–
1
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45%) could be obtained using pyridyl or quinolinyl as functional
group. Switching to photo-induced condition (450–455 nm, 40
oC), we observed a dramatic functional group effect where only
quinolinyl-substituted substrate 1c delivered the expected cross
coupling product in 80% yield. These initial results indicated that
the functional group plays a bifunctional role as a directing group
and as an energy transfer promoter.
any desired product, which indicates the unique property of Rh
in the photo-induced decarbonylative reactions (entries 16–18).
Considering the mild nature of the photo-induced
decarbonylative coupling, a light on/off experiment was carried
out to get the reactivity profile of this reaction (see Table S3 and
Figure S1 in Supporting Information for light on/off experiment).
It revealed that constant irradiation was required for effective
product formation versus light on/off experiment. No background
product formation during dark exposure supports that the current
protocol does not involve a light-initiated radical chain pathway.
Table 1. Selected optimization studies.
With the optimized conditions in hand, the generality of alkyne
substrates was subsequently tested. As depicted in Table 2a,
various symmetrical diarylacetylenes bearing either electron-
withdrawing or electron-donating substituents all successfully
afforded isoquinolones with moderate to excellent yields (3ca-
3cf). Notably,
a bromo-bearing aryl-alkyne could be well
tolerated and delivered isoquinolone 3cb in 95% yield.
Interestingly, an alkyne with a cyano-functional group at the
para-position of the phenyl ring was a bit sluggish in this protocol
(3cd). This presumably ascribed to the coordinated ability of
cyano-groups to rhodium. Due to the steric hindrance of ortho-
substituted diarylalkyne, isoquinolinone 3cf was isolated as a
5:1 rotamer mixture in 67% yield. To our delight, dialkyl
acetylenes were also applicable under this visible light-induced
rhodium catalysis conditions and led to 3cg-3ci in 63–83%
yields. Encouraged by these promising results, a series of aryl-
substituted terminal alkynes were further examined in this
transformation. To our delight, these reactions exclusively
produced isoquinolones 3cj-3cm in 28–42% yields, which is
uncommon due to the existence of
a dominant [2+2+2]
cycloaddition side reaction.[19] For alkyl-substituted terminal
alkynes such as acetylene, cyclohexylacetylene, 1-decyne, no
product was formed under the photo-induced condition (see
Scheme S1 in Supporting Information). Furthermore,
unsymmetric alkynes were also suitable substrate to generate
3cn-3ct in moderate to high yields with acceptable
regioselectivities. It is noteworthy that ethyl 3-phenylpropynoate
(2u) led to 4-substituted isoquinolone 3cu in 36% yield. This
unique regioselectivity is probably due to electron-withdrawing
ability of the ester group. No expected decarbonylative coupling
was observed for alkene substrates such as phenylmaleimide,
methyl cinnamate or styrene (see Scheme S1 in Supporting
Information).
To further improve the reactivity, a systematic optimization of
this photo-induced cross coupling reaction was carried out
(Table 1 and Table S1-S2 in Supporting Information). After
careful evaluation of the reaction conditions, isoquinolone 3ca
was formed in 90% yield using [RhCl(C2H4)2]2 as the catalyst
precursor under blue light irradiation (430–435 nm) at 40 oC
(Table 1, entry 1). Control experiments confirmed the essential
roles of the rhodium and the visible light (entries 2 and 3). It was
found that photoreaction showed higher efficiency than thermal
induced reaction (entry 4). Except for Wilkinson’s catalyst
RhCl(PPh3)3, other RhI precursor, such as Rh(acac)(CO)2,
[RhCl(CO)2]2, [RhOH(COD)]2 and [RhCl(COD)]2 showed
comparable reactivity (entries 5–9). Both DCE and PhCl could
serve as competent solvents (entries 10 and 11). Further
screening of wavelengths revealed that 430–435 nm was the
optimal wavelengths for this protocol, may be related to the
maximum absorption wavelength of rhodium intermediates
(entries 12 and 13). To our delight, the decarbonalytion reaction
proceeded well at 30 oC, which suggested that the light induced
reaction could be carried out at room temperature (entry 14). A
high yield was also obtained at lower catalyst loadings (1.0
mol%) with a prolonged reaction time (entry 15). Notably, other
commonly used transition-metal catalysts for decarbonylation,
such as Ni(COD)2,[9a-d, 9g] Co2(CO)8,[18] Pd(PPh3)4,[8] did not afford
Next, we further investigated the scope of phthalimides (Table
2b). Substrate possessing methoxy group on the 6-position of
quinoline ring successfully furnished the desired product 3da in
89% yield. Symmetric phthalimides reacted with 2a smoothly in
this process, providing the corresponding products 3ea and 3fa
in 74–92% yields. Substrate bearing tert-butyl group at the 4-
position (1g) exhibited good reactivity via this decarbonylation
process, although gave a mixture of two regioisomers 3ga and
3ga' in approximate 1:1 ratio. In the case of 3-fluorine
substituted phthalimide, the product 3ha was isolated in 69%
yield, together with a 5:1 regiomeric ratio. Remarkably,
phthalimides having substitutents at the 3-position, such as 3-
chloride and 3-alkoxy groups, all worked well to give
2
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Table 2. Substrate scope for photo-induced decarbonylative coupling of imides with alkynes.a
regiospecific isoquinolones 3ia-3la in 50–81% yields. The
molecular structure of 3ja was confirmed by X-ray
crystallography. Of particular interest is that these reactions all
exclusively occurred at the adjacent positions of the
corresponding substituents, which offers an important
complement for the reported C–H activation strategy in the
synthesis of 5-substituted isoquinolinones.[20]
unexpected coordination saturated complex Rh-2 (18-electron).
1
The structure of Rh-2 was fully characterized by H, 13C NMR
and HRMS (See Supporting Information). In the absence of
visible light irradiation, no red precipitate was formed and only
phthalimide 1c was recovered in 72% yield. The UV/Vis
absorption spectra of the Rh-2 showed a strong absorbance in
the region of 390–420 nm (Scheme 3b). The catalytic
performance of Rh-2 complex was evaluated for the
decarbonylative coupling of imide 1c with alkyne 2a (Scheme
3c). No desired product was observed in the absence of light.
Under light irradiation, 3ca was obtained in 8% yield with 2.7
turn over number (TON). The low yield probably results from the
different coordination environment between Rh-2 complex and
real Rh catalyst. Overall, these above results suggest that
Regarding mechanistic features, a key question is elucidating
the role of visible light. First, the effect of light on the synthesis
rhodium intermediate was investigated (Scheme 3a). Under light
irradiation, the reaction of [RhCl(C2H4)2]2 with phthalimide 1c
slowly generated a red solid precipitate which was then treated
with excess pyridine to form a more stable speculative complex
Rh-1. The subsequent purification of Rh-1 (16-electron) gave an
3
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rhodium complex simultaneously serves as the catalytic center
and photosensitizer for decarbonylation.
cleaves the C–C bond to give Rh-complex C. Under visible light
irradiation, it generates the excited state Rh-complex C* where
the transfer of an electron from the π-backbonding Rh-CO orbital
into an antibonding orbital decreases the bond dissociation
energy of the Rh–CO bond. This leads to the subsequent CO
extrusion under mild conditions to give a Rh intermediate D with
a vacant coordination site. The coordination and migratory
insertion of the alkyne 2 with D delivers a seven-membered
rhodacycle E, which undergoes reductive elimination to form the
isoquinolone 3 and regenerates the RhI catalyst A.
a) Effect of light on the synthesis of rhodium intermediate.
O
O
O
1) hv, DCE
30 oC, 18 h
2) pyridine
30 oC, 4 h
N
N
N
Et3N
Cl
Cl
III
III
Rh
N
Rh
N
N
O
Py
Et3N
Py
Rh-2: 35% yield
Rh-1
1c (0.1 mmol)
+
O
N
Cl
O
N
Rh
Rh
1) w/o hv, DCE
30 oC, 18 h
2) pyridine
Cl
Cl
III
+
(0.05 mmol)
Rh
N
N
O
In summary, we have developed a visible light-induced
rhodium catalysis for decarbonylative coupling of imides with
alkynes under ambient conditions. The main advantages include
mild conditions, good regioselectivity, and wide functional group
tolerance. Initial mechanistic studies suggest that rhodium
complex simultaneously serves as the catalytic center and
photosensitizer for decarbonylation. This visible light-promoted
catalytic decarbonylation strategy offers new opportunities for
reviewing old transformations with ligand dissociation as a rate
determining step.
30 oC, 4 h
Py
Rh-1: not observed
1c: 72% (recovery)
b) UV/Vis absorption spectra of Rh-2 and [RhCl(C2H4)2]2 (labeled as Rh cat.).
O
N
Cl
Rh
III
N
Et3N
Py
Rh-2
Cl
Rh
Rh
Cl
Rh cat.
Acknowledgements
We thank Prof. Yong-Gui Zhou (DICP) and Prof. Daniel K. Kim
(Temple University) for helpful discussion and paper revisions.
Financial support from the National Natural Science Foundation
of China (21971234, 21772194, 21572225), China Postdoctoral
Science Foundation (2019M661137) and Liaoning Revitalization
Talents Program (XLYC1807181) is acknowledged.
c) Catalytic process using intermediate Rh-2 as the catatyst.
O
O
Ph
[Rh]-2 (3.0 mol%)
N
N
+
40 oC, DCE, 18 h
N
Ph
N
O
Ph
Ph
with light: 3ca: 8% yield
w/o light: 3aa: 0% yield
1c (0.1 mmol)
0.12 mmol
3ca
Scheme 3. Mechanistic studies on reaction intermediate.
Keywords: visible light • bifunctional rhodium catalysis • C-N
bond cleavage • decarbonylative coupling • alkynes
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5
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A visible light-induced rhodium catalysis has been developed for decarbonylative coupling of imides with alkynes under ambient
conditions. Initial mechanistic studies suggest that the rhodium complex simultaneously serves as the catalytic center and
photosensitizer for decarbonylation.
Visible Light-Induced Bifunctional Rhodium Catalysis for Decarbonylative Coupling of Imides
with Alkynes
Xiang-Ting Min, Ding-Wei Ji, Yu-Qing Guan, Shi-Yu Guo, Yan-Cheng Hu, Boshun Wan, Qing-An Chen*
6
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