Photoredox mediated nickel catalyzed C(sp3)-H thiocarbonylation of ethers

Article abstract of DOI:10.1039/c7sc02516e

The first direct C(sp³)-H thiocarbonylation reaction is achieved by visible light photoredox/Ni dual catalysis. The thioester group of thiobenzoate is transferred to the α-oxy carbon of various cyclic/acyclic ethers, which is the opposite to the commonly expected chemical reactivity involving acyl group transfer via the weaker C(acyl)-S activation. Through mechanistic studies, we proposed that the reaction is initiated by photocatalytic reduction and fragmentation of the thioester into an acyl radical and a thiolate. A nickel complex binds to the thiolate and induces the decarbonylation of the acyl radical to form an aryl radical, which abstracts hydrogen from the α-oxy carbon of the ether. The resulting α-oxy C(sp³) centered radical re-binds to the (RS)(CO)Ni complex, which undergoes CO migratory insertion and reductive elimination to give the desired thioester product.

Full text of DOI:10.1039/c7sc02516e

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Photoredox Mediated Nickel Catalyzed C(sp3)–H
Thiocarbonylation of Ethers
Byungjoon Kang and Soon Hyeok Hong*
Received 00th January 20xx,
Accepted 00th January 20xx
The first direct C(sp3)–H thiocarbonylation reaction is achieved by visible light photoredox/Ni dual catalysis. Thioester group
of thiobenzoate is transferred to α-oxy carbon of various cyclic/acyclic ethers, opposite to the commonly expected chemical
reactivity involving acyl group transfer via the weaker C(acyl)–S activation. Through mechanistic studies, we proposed that
the reaction is initiated by photocatalytic reduction and fragmentation of the thioester into acyl radical and thiolate. A nickel
complex binds to the thiolate and induces decarbonylation of the acyl radical to form an aryl radical, which abstracts
hydrogen from α-oxy carbon of ether. The resulting α-oxy C(sp3) centered radical rebounds to (RS)(CO)Ni complex, which
undergoes CO migratory insertion and reductive elimination to give the desired thioester product.
DOI: 10.1039/x0xx00000x
www.rsc.org/
coenzyme B12 catalyse L-methylmalonyl-CoA to succinyl-CoA
isomerization by radical generation on an sp3 hybridized carbon
followed by intramolecular 1,2-migration of the thioester group
(Scheme 1A).11 However, to the best of our knowledge, a direct
thioester group transfer reaction to a C–H bond has never been
achieved in organic synthesis. To address the challenge, we
envisioned an unprecedented C(sp3)–H thiocarbonylation
utilizing simple thioester molecules as the thioester group
source.
Introduction
Thioesters are versatile synthetic building blocks1 and
convenient protecting groups for thiols in organic synthesis.2 As
an activated analogue of alcohol-derived ester, it can be easily
transformed into ester, amide, and ketone. In Nature, the
thioester group plays critical role in metabolism3 and cellular
function regulation.4 The thioester moiety also serves central
role in Native Chemical Ligation (NCL)5 and Expressed Protein
Ligation (EPL)6 in the biological sciences.
Due to its versatility, the direct and selective incorporation of
a thioester group into the desired position of a molecule has
high synthetic value. The most common method for thioester
synthesis is a reaction between a thiol and an activated
carboxylic acid, or the coupling of a thioacid and an electrophile
(Scheme 1A).7 However, the requirement of high oxidation state
carbon-based reactants, harsh reaction conditions, and
sensitivity of thiols towards oxidation limit the utility of the
reactions. Several alternative synthetic methods have been
developed including the oxidative thioesterification of
aldehydes8 and thiocarbonylation of alkenes9 or organic
halides10 with carbon monoxide gas. Most of these
methodologies still require a thiol and a suitable coupling
partner as the reactants, sharing similar limitations of the
classical syntheses.
Direct C–H thiocarbonylation can serve as an ideal approach
for thioester synthesis. Indeed, Nature utilizes an inspiring C–H
functionalization strategy for the synthesis of metabolically
important thioesters. Methylmalonyl-CoA mutase (MCM) and
Department of Chemistry, College of Natural Sciences, Seoul National University, 1
Gwanak-ro, Seoul 08826, South Korea. E-mail: soonhong@snu.ac.kr
† Electronic supplementary information (ESI) available: Experimental details and full
characterization of substrates and products. Crystallographic data for compound
[Ni-II]. CCDC 1516709. For ESI and crystallographic data in CIF or other electronic
format see DOI:
Scheme 1. Thioester synthesis
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The biggest hurdle for the thioester group transfer reaction is indicating the NHC bound nickel complex acted as the
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DOI: 10.1039/C7SC02516E
relative weakness of C(acyl)–S bonds as compared to C(acyl)–C catalytically active species (entry 8). In addition, a good yield
bond (Scheme 1B). Indeed, to the best of our knowledge, all with full conversion was also obtained in a shortened reaction
literature examples concerning the oxidative addition of time of 4 h (entry 10).
organometallic complex into thioesters show that the reaction
preferably occurs in C(acyl)–S bond to give acyl–metal
complex.12 We could not find any example on selective C–C(acyl)
bond activation in a thioester. Nevertheless, we initially
postulated that selective activation of the C–C(acyl) bond could
be achieved by controlling the electronic and steric character of
the thioesters, motivated by the cases of selectivity control of
C(aryl)–O vs C(acyl)–O bond activation in esters.13 The theory
was eventually proven incorrect.
Recently, visible light photoredox/transition metal dual
catalysis14 has been utilized for selective sp3 C–H
functionalization. The examples showed that even weakly
reactive α-amino15 and α-oxy15d, 16 C(sp3)–H bonds could be
functionalized. We devised a strategy to merge photoredox
driven C–H functionalization with transition metal mediated
thioester activation. Specifically, we focused on the α-oxy
C(sp3)–H thiocarbonylation reaction, since α-oxy carboxylic acid
derivatives are key functional groups in some pharmaceuticals
such as selexipag or cetirizine. Herein, we report the first
chemo-selective α-oxy C(sp3)–H thiocarbonylation reaction
with a newly proposed photoredox/Ni dual thioester activation
strategy (Scheme 1C).
Table 1 Optimization of reaction conditionsa
Entry Reaction conditions
t (h)
12
12
12
12
12
12
12
12
12
4
Yield of (%)b
1
As shown
90c
2
Ar = Ph (1u)
7
2
49
0
0
0
60
<1
3
4
Ar = (p-Me)Ph (1v)
Ar = C6F5 (1w)
5
6
No NiCl2·glyme
No SIPr·HCld
7
8
9
10
No Ir[dF(CF3)ppy]2(dtbbpy)PF6
SIPr instead of SIPr·HCl with no K2CO3
Ni(COD)2 instead of NiCl2·glyme
As shown
89 (83e)
a Reaction conditions: thioester (0.25 mmol), NiCl2·glyme (5 mol%), SIPr·HCl (10
mol%), K2CO3 (1 equiv), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol%), and THF (2.5 mL)
in 4 mL vial irradiated with a 34 W Blue LED. b GC yield using dodecane as
internal standard. c α,α,α-Trifluorotoluene (75%) was observed. d SIPr·HCl = 1,3-
bis(2,6-diisopropylphenyl)imidazolinium chloride. e Isolated yield.
With the optimized conditions in hand, diverse aryl thioesters
were applied for the thiocarbonylation reaction of THF (Table 2).
A range of aryl thioesters with alkyl substituents in the p-, m-
Results and Discussion
Recently, Doyle and co-workers succeeded in reacting an N-aryl
amine with a 2-pyridylthioester under photoredox/Ni dual
catalytic conditions (Scheme 1B).15a In this case, only the C–H
acylation product via activation of the weaker C(acyl)–S bond
was observed. To preferably activate the C(acyl)–C bond instead,
we hypothesized that increasing the electron deficiency of the
acyl group of the thioester could selectively weaken the C(acyl)–
C bond. Indeed, an electron deficient thioester 1a showed
reasonably high reactivity toward the target reaction (Table 1,
Table S1). After intensive optimizations (Table S2), an excellent
yield (90%) of 3aa was obtained using an N-heterocyclic carbene
(NHC) based Ni(II) complex with Ir[dF(CF3)ppy]2(dtbbpy)PF6 as a
visible light photoredox catalyst in THF (2a) (Table 1, entry 1).
The only detected side product was 4-trifluoromethyl diphenyl
sulfide (4a), which was possibly formed by decarbonylation
process.17 It should be emphasized that the thioester product
was solely formed without generation of α-oxy C–H acylation
product.15a The reactivity highly depends on the electronic
nature of thioesters. Among those tested, only thiobenzoate
derivatives exhibited the desired activity (Table S1). A dramatic
decrease in yield was observed when relatively electron rich
acyl groups were used (Table 1, entries 2–3), while the
pentafluorophenyl group gave a moderate yield (entry 4).
Control experiments showed that Ni catalyst, NHC precursor,
and photoredox catalyst are essential components of the
reaction (entries 5–7). When the separately prepared N-
heterocyclic carbene (NHC) SIPr was used as an additive, a
moderate yield was obtained without the use of additional base,
and o-positions gave good yields of the desired products (3ba
–
3ea). Alkoxy groups in the substrate did not mediate any side
reactions, presumably due to the higher amount of the THF
radical (3fa
–3ha). A thioether group was also tolerated (3ia).
Fluorine-containing thioesters showed excellent reactivity (3ja
–
3la). Encouragingly, C–N and C–O unsaturated bonds did not
induce any side reactions or interfere with the catalytic
reactivity (3ma
–3oa). Naphthyl thioesters reacted smoothly,
although 1-naphthylthioester gave a decreased yield (3pa
,
3qa).
Notably, an aryl boronate, which can be further functionalized,
was also tolerated under the reaction conditions (3ra). Finally,
a benzyl thioester was successfully transferred to the α-oxy
carbon of THF (3sa, 3ta). However, aliphatic thioesters did not
exhibit any reactivity under the described reaction conditions.
Next, the scope of ethers was investigated (Table 3). Selective
and efficient reactions occurred in the α-oxy position of
common cyclic ether solvents such as tetrahydropyran (3ab
)
and 1,4-dioxane (3ac). In the case of ethers in which the
solubility of the Ni complex is poor, acetonitrile was adopted as
a co-solvent. Diethylether (2d) underwent thiocarbonylation
moderately (3ad). The use of anisole (2e) or tert-butyl methyl
ether (MTBE, 2f) gave the desired products in low yields (3ae
,
3af), possibly due to the relatively low stability of the primary
alkyl radical compared to its secondary analogue. Other
heterocycles such as thiophene and N-protected pyrrolidines
(N-methyl, N-phenyl, and N-Boc) were tested as reactants using
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acetonitrile or DMA as the co-solvent due to solubility issue, and energy (BDE) of C–C(acyl) bond with that of the C–S bonds as a
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no conversion was observed.
preliminary tool like in the Ni catalyzed C(aryl)–O vs C(acyl)–O
bond activation in ester.13d Differently from our expectation of
significantly lowed BDE of C–C(acyl) bond in electron deficient
thioester 1a, the calculated BDE of the C–C(acyl) bond of
thioester 1a is still much higher than that of the C–S bonds
(Table S3). Also, the BDE cannot explain the unique reactivity of
1a among various thioesters since no significant difference
among thioesters was found. In pursuit of an alternative
pathway, a mechanism initiated by oxidative addition of Ni(0)
into the C(acyl)–S bond was considered. Followed by
decarbonylation and migratory insertion of CO into the Ni–S
bond, it might generate a thiocarbonyl Ni intermediate.
However, Holm and Tucci reported that CO migratory insertion
preferably occurred to Ni–C bond over a Ni–S bond in
[Ni(bpy)(R’)(SR)] complexes.18 Moreover, we found that
Ni(COD)2, a commonly used Ni(0) complex which has high
oxidative addition activity, did not mediate the desired reaction.
Instead, a significant amount of decarbonylation product 4a
was formed (Table 4). To identify active catalytic intermediates,
syntheses of monomeric NHC-Ni(I) and Ni(II) complexes were
Table 2 Substrate scope of thioestersa
attempted, but unsuccessful. Instead, catalytic activities of the
19
reported NHC-Ni dimer complexes [(SIPr)NiCl]2 ([Ni-I]
[(SIPr)NiCl]2(μ-Cl)2 ([Ni-II]
)
and
)
20 were investigated to get insight on
the oxidation state of Ni during the reaction (Table 4).21 With
[Ni-I], the decarbonylation product 4a was observed as the
major product (29%) with 5% of 3aa. On the contrary, well-
defined NHC-Ni(II) dimer complex [(SIPr)NiCl]2(μ-Cl)2 ([Ni-II])
produced the C–H thiocarbonylation product 3aa (11%) more
than 4a (8%).
Because the tested Ni complexes exhibited significantly
lowered conversions, we retested the catalytic activity in
a Reaction conditions: thioester (0.25 mmol), NiCl2·glyme (5 mol%), SIPr·HCl (10
mol%), K2CO3 (1 equiv), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol%), and THF (2.5 mL)
b
in
4
mL vial irradiated with
a
34
W
Blue LED.
2 mol% of
Ir[dF(CF3)ppy]2(dtbbpy)PF6 was used.
presence of 1 mol% of NiCl2·glyme (Table 4, entries 4–7). Under
the conditions, difference in catalytic ability of Ni(0), Ni(I), and
Ni(II) becomes more significant. While addition of 5 mol% of
Ni(0) or Ni(I) does not facilitate the formation of 3aa, presence
of NHC-Ni(II) species gave meaningful improvements in
reactivity, implying that Ni(II) could be the major catalytically
active species.
Table 3 Substrate scope of ethersa
Table 4 Catalytic activity of nickel complexes
a
Reaction conditions: 1a (0.25 mmol), NiCl2·glyme (5 mol%), SIPr·HCl (10
mol%), K2CO3 (1 equiv), Ir[dF(CF3)ppy]2(dtbbpy)PF6 (1 mol%), and ether (2.5 mL)
in 4 mL vial irradiated with a 34 W Blue LED. b Ether (2.5 mL) is mixed with
CH3CN (0.5 mL).
a With SIPr·HCl (10 mol%) and K2CO3 (1 equiv).
From mechanistic investigations, we realized that the initial
hypothesis on preferable C–C(acyl) bond activation by Ni
complex should be reconsidered. To obtain insight of relative
bond strengths, we compared calculated bond dissociation
The results indicate that oxidative addition type C–C(acyl) or
C(acyl)–S bond activation by electron rich Ni(0) or Ni(I) did not
lead to the formation of the desired product in our reaction.
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Another possible thioester activation pathway is single electron process,27 although formation of an aryl radical from an aryl acyl
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28
DOI: 10.1039/C7SC02516E
reduction of the thioester. It is known that thioesters can be radical with CO exclusion would be difficult. To prove the
electrochemically reduced and fragmented into acyl radicals generation of a Ni–CO intermediate during the reaction, we
and thiolates.22 The same process could be mediated by performed a reaction under a 13CO atmosphere utilizing a two-
photoredox catalysis in our system. To check the validity of this chamber reactor developed by Skrydstrup et al. (Fig. S1).29
hypothesis, cyclic voltammetry (CV) of 1a was measured (Fig. significant amount of 13C incorporation in the acyl carbon of 3aa
A
S5). The results show an irreversible reduction peak [1a/
1a–] at was observed, indicating that a Ni–CO intermediate is formed
red
EP = –1.96 V vs Ag/AgNO3 (0.01 M) electrode in CH3CN during the course of the reaction (Scheme 2B). The aryl radical
(correlated to –1.65 V vs saturated calomel electrode (SCE) in is highly reactive so that it can abstract a hydrogen from the
CH3CN). The significantly lower reduction potential of 1a as relatively weak α-oxy carbon of THF as the next step.16a The role
compared to aliphatic thioesters and other relatively electron of aryl radial as hydrogen abstraction reagent was confirmed by
rich aryl thioesters could be the reason for the unique reactivity generation of α,α,α-trifluorotoluene-d (4a-d) in case that the
of 1a 23 1a–] is higher than reaction was performed in THF-d8 (Fig. S3). The resulting α-oxy
. Although the reduction potential [1a/
that of the possible reductant Ir(II) (E1/2red[Ir(III)/Ir(II)] = –1.37 V alkyl radical adds to the Ni(III) complex to give Ni(IV). Migratory
vs SCE in CH3CN),24 a small portion of reduction wave overlap insertion of the CO ligand followed by reductive elimination can
may induce single electron transfer at a meaningful rate produce the desired thioester, regenerating the Ni(II) species.
considering that an irreversible fragmentation may occur after Although it is still difficult to rule out the possible more general
reduction of the thioester. Also, it has been proposed that Ni(I)-Ni(III) cycle, we prefer the proposed a Ni(II)-Ni(IV) cycle
cationic character of photoredox catalyst may electrostatically based on the experiments in Table 4.
stabilize the generated radical anion, facilitating reduction
process.25 Additionally, in the optimized reaction conditions,
there is a chance that complexation of thioester and nickel
complex can facilitate the thioester reduction process. To prove
this hypothesis, a CV experiment of thioester was conducted in
presence of stoichiometric amount of a Lewis acid. Mg(II) cation
is utilized because it has redox-inactive character within scan
range (Ered = -2.61 V vs SCE in H2O) and has similar ionic radii (72
pm) compare to that of Ni(II) (69 pm).26 Indeed, reduction peak
shift from -1.65 V to -1.21 V (vs SCE) was observed (Fig. S6). To
further validate this reduction process by capturing the in situ
generated acyl radical, methyl acrylate was added to the system
in absence of a Ni complex (Scheme 2A). The coupling product
5a was isolated in 26% yield, confirming that the proposed
photocatalytic fragmentation of the thioester can happen.
Fig. 1. Proposed mechanism.
Conclusions
The first selective C(sp3)–H thiocarbonylation reaction is
achieved. It is the first example of utilizing simple thioester
molecules as the thioester group source in thiocarbonylation
reaction, avoiding use of CO gas. Diverse aryl and benzyl
thioesters could be synthesized in high yields. An iridium
photoredox catalyst mediated electron transfer between a
Scheme 2. Mechanistic studies
nickel complex and the thioester comprises the key step of the
reaction. The developed direct C–H thiocarbonylation reaction
will serve as a novel strategy to synthesize biologically and
synthetically important thioesters under mild conditions.
Based on this rationale, a revised mechanism is proposed (Fig.
1). Initially the photo-activated Ir[dF(CF3)ppy]2(dtbbpy)PF6
red
complex (E1/2 [*Ir(III)/Ir(II)] = +1.21 V vs SCE in CH3CN)24
red
oxidizes a model NHC-Ni(II) species (EP
[ /[Ni-II]] = +1.01
[Ni-II]+
V vs SCE in CH3CN) to Ni(III) (Fig. S7). The resulting Ir(II) complex
reduces the thioester and returns to Ir(III). The reduced
thioester is then fragmented into an aryl acyl radical excluding
the thiolate, which can be immediately captured by Ni(III). The
resulting aryl acyl radical is proposed to undergo Ni mediated
decarbonylation to give the aryl radical. There have been a few
reports that transition metal catalysts can mediate this
Acknowledgements
We thank J. G. Lee in the Prof. T. D. Chung group for the help of
cyclic voltammetry analysis. This work was supported by
Samsung Science and Technology Foundation under Project
Number SSTF-BA1601-12. B. Kang was supported by the Global
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Chemical Science
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DOI: 10.1039/C7SC02516E
The first C(sp3)–H thiocarbonylation is achieved by visible light photoredox/Ni dual catalysis using
thiobenzoates as the thioester group source.