Controlled Ni-catalyzed mono- and double-decarbonylations of α-ketothioesters

Article abstract of DOI:10.1039/c8cc09352k

A method for Ni-catalyzed controlled decarbonylation of α-ketothioesters is described. Mono- and double-decarbonylations, which gave thioesters and thioethers, respectively, were selectively achieved by changing the ligand. A fundamental study of Ni-catalyzed decarbonylation of α-ketothioesters is presented.

Full text of DOI:10.1039/c8cc09352k

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
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DOI: 10.1039/C8CC09352K
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Controlled Ni-catalyzed mono-and double-decarbonylations of α-
ketothioesters
Received 00th January 20xx,
Accepted 00th January 20xx
Zhao-Jing Zheng,a Chen Jiang,b Peng-Cheng Shao,b Wen-Fei Liu,b Tian-Tian Zhao,b Peng-Fei Xu*a
and Hao Wei*b
DOI: 10.1039/x0xx00000x
www.rsc.org/
A method for Ni-catalyzed controlled decarbonylation of α- intermediates in the production of various pharmaceuticals
ketothioesters is described. Mono- and double-decarbonylations, and bioactive molecules.13 Because of their vast potential,
which gave could thioesters and thioethers, respectively, were much attention has focused on the synthesis of these
selectively achieved by changing the ligands. A fundamental study compounds in recent years. They can be prepared from methyl
of Ni-catalyzed decarbonylation of α-ketothioesters is presented.
2-phenylacetate,14 cyano keto phosphoranes,15 α-aryl halo
derivatives,16 1,3-diones,17 terminal alkynes,18 α-hydroxy
esters,19 aldehydes,20 and other compounds.21 In this report,
we present a Ni-catalyzed, controlled decarbonylation of α-
ketothioesters. The use of different ligands enabled mono- and
double-decarbonylations to be selectively achieved, to give
thioesters and thioethers, respectively (Scheme 1C).
The formation of C–S bonds is of fundamental importance in
organic chemistry because sulfur-containing motifs form part
of various natural products and pharmaceutical agents.1
Despite the robustness of classical protocols for the synthesis
of C–S bonds,2 the development of alternative methods,
particularly catalytic synthetic routes, is still a formidable
challenge. Intramolecular CO extrusion–recombination
reactions provide a powerful methods for the formation of
chemical bonds.3 In the past few decades, advances in
decarbonylative bond formation, which can be used to create
C–C,4 C–P,5 C–N,6 C–Cl,7 and C–O,8 bonds through transition-
metal catalysis, have been made (Scheme 1A). Recently, the
groups led by Sanford,9a Szostak,9b and Yamaguchi9c
independently developed methods for the Ni-catalyzed
intramolecular decarbonylative conversion of thioesters to
thioethers. This provides a valuable alternative to traditional
cross-couplings in the construction of C–S bonds (Scheme 1B).
In view of the unique nature of thioester decarbonylation,10
we considered whether such an activation mode could be
extended to α-ketothioesters. The challenges are two-fold. (1)
Mono- and double-decarbonylations of 1,2-dicarbonyl
compounds are competing reactions, therefore controlled
activation of the α-ketothioesters must be achived catalytically.
(2) Unlike thioesters, ketothioesters with two electrophilic
carbon centers can undergo facile thiolate transfer11 and
cyclization,12 therefore chemoselectivity is difficult to achieve.
Derivatives of α-keto acids are valuable precursors and
A
Transition-metal-catalyzed decarbonylative C X bond formation

O
catalyst
R
X
R
X
X = C, O, N, P, S
B
Decarbonylation of thioesters (Sanford, Szostak and Yamaguchi 2018)
O
Ni catalyst
Ar SR
Ar
SR
C
Controlled Ni-catalyzed decarbonylation of -ketothioesters (this work)

O
O
cat. Ni
cat. Ni
SR
Ar SR
Ar
ligand 1 Ar
SR
ligand 2
O
Scheme 1. Ni-catalyzed, controlled decarbonylation of α-ketothioesters
The reactivities of α-ketothioesters were investigated by using
S-phenyl 2-oxo-2-phenylethanethioate (1a) as
a model
substrate. Initially, Ni(cod)2/ligand combinations that have
previously been successfully used in Ni-catalyzed direct
decarbonylation of ketones4f and thioesters9a were used as
catalysts (Table 1). As anticipated, the efficiency was strongly
a. State Key Laboratory of Applied Organic Chemistry College of Chemistry and
Chemical Engineering, Lanzhou University, Lanzhou 730000, China.
b. Key Laboratory of Synthetic and Natural Functional Molecular Chemistry of the
Ministry of Education, National Demonstration Center for Experimental Chemistry
Education (Northwest University), College of Chemistry & Materials Science,
Northwest University, Xi’an 710127, China.
† Electronic Supplementary Information (ESI) available: Experimental procedures,
mechanistic details, spectroscopic data and copies of 1H and 13C NMR spectra. See
DOI: 10.1039/x0xx00000x
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dependent on the nature of the ligand. Reactions using
phosphine ligands afforded thioesters in high yields (Table 1,
entries 1 − 3); the best ligand was PPh3, which provided the
mono-decarbonylated product in 85% yield (Table 1, entry 2).
Further optimization focused on using different solvents;
switching the solvent from toluene to dioxane or
chlorobenzene did not provide a better yield (Table 1, entries 4
and 5). We then evaluated a series of N-heterocyclic carbene
(NHC) ligands with the expectation that their strong σ-donor
conventional cross-coupling reactions. Finally, this protocol
was extended to the polyaromatic compound 2m; the desired
product was obtained in good yield.
View Article Online
DOI: 10.1039/C8CC09352K
Table 2 Scope of mono-decarbonylation of α-ketothioesters.
a,b,c
Ni(cod)2 (10 mol%)
O
O
PPh3 (20 mol%)
S
R2
R1
R2
R1
S
toluene
O
O
150 oC, 15 h
properties
would
facilitate
the
required
double
Me
tBu
decarbonylation. Among the NHCs examined, IPrMe was the
most effective; the desired doubly decarbonylated product 3a
was isolated in 40% yield (Table 1, entry 9). Changing the
solvent to dioxane and prolonging the reaction time to 22 h
gave further improvements and 3a was isolated in 77% yield
(Table 1, entry 10). Reactions performed in the presence of
Pd[P(o-tol)3]2/dppf (Table 1, entry 11)9b or Pd(PPh3)4 (Table 1,
entry 12),10b both of which have been reported to catalyze
decarbonylation of thioesters, did not produce any 3a or gave
3a in a low yield. Molecular sieves have been reported to
greatly enhance Pd-catalyzed decarbonylation of aldehydes
because of their ability to remove trace amounts of water,22
but in our reaction the addition of molecular sieves was not
necessary.
O
S
O
S
S
2b
2e
2c
82% (6:1)
86% (>20:1)
2a
85% (13:1)
OMe
F
Cl
O
S
O
S
O
S
2f
82% (>20:1)
2d
63% (>20:1)
80% (11:1)
Br
O
S
O
S
Me
O
S
iPr
2i
84% (10:1)
2g
2h
2k
87% (9:1)
83% (>20:1)
O
S
O
S
O
S
MeO
MeO
MeOOC
Table 1 Optimization of reaction conditions.a
MeO
2l
82% (7:1)
84% (15:1)
2j
71% (12:1)
Ni(cod)2 (10 mol%)
O
O
S
O
Ligand (20 mol%)
S
Ph
Ph
Ph
+
Ph
Ph
S
Ph
S
Solvent, 150 oC, 15 h
O
2m
84% (12:1)
1a
2a
3a
aStandard conditions: 1 (0.2 mmol), Ni(cod)2 (10 mol%), PPh3 (20 mol%),
entry
1
ligand
PCy3
PPh3
dppe
PPh3
PPh3
solvent
2a, yieldb (%)
3a, yieldb (%)
c
toluene (2 mL), 150 °C, 15 h. bIsolated yields. Mono-decarbonylation:double
toluene
81
85
52
74
79
52
53
50
48
<5
84
16
<5
<5
31
18
12
25
20
36
40
77
<5
0
-decarbonylation selectivities are given in parentheses.
2
toluene
The scope of the double-decarbonylation reaction was also
explored (Table 3). Various substituents, including some with
electron-donating (3b and 3c), or electron-withdrawing (3e
and 3g) properties, on the thiol-derived fragment were well
tolerated; the desired adducts were obtained in moderate to
good yields (57%–77%). Finally, the scope of the reaction with
different carboxylic acid-derived portions was briefly
examined. A selection of sterically-hindered (3h), electron-
deficient (3j), and electron-rich (3k and 3l) substrates were
converted into the desired thioethers in good yields. Recently,
Yamaguchi and Itami reported a Ni-catalyzed decarbonylative
etherification of aromatic esters.7 We were intrigued to find
that these Ni-catalyzed decarbonylations proceeded in the
presence of the sensitive aryl ester linkage; this shows the
high chemoselectivity of the present method.
3
toluene
4
dioxane
chlorobenzene
toluene
5
6c
7c
8c
IMes.HCl
IMesMe.HCl toluene
IPr.HCl
IPrMe.HCl
IPrMe.HCl
dppf
toluene
toluene
dioxane
toluene
toluene
9c
10c
11d
12e
-
Me
Me
N
R
N
PPh2
R
N
N
Ph2P
PPh2
Fe
R
R
Ph2P
IMesMe (R = 2,4,6-Me3C6H2)
IPrMe (R = 2,6-iPr2C6H3)
IMes (R = 2,4,6-Me3C6H2)
IPr (R = 2,6-iPr2C6H3)
dppe
dppf
Table 3 Scope of double-decarbonylation of α-ketothioesters
aReaction conditions: 1a (0.2 mmol), Ni(cod)2 (10 mol%), ligand (20 mol%),
solvent (2 mL), 150 °C, 15 h. bIsolated yields. cCs2CO3 (20 mol%), 22 h. dPd[P(o-
tol)3]2 in place of Ni(cod)2 . e Pd (PPh3) 4 in place of Ni(cod)2.
a,b,c
Ni(cod)2 (10 mol%)
IPrMe.HCl (20 mol%)
O
Cs2CO3 (20 mol%)
R1
R2
S
R1
R2
S
Dioxane
150 oC, 22 h
O
Having established the optimum conditions, we then
investigated the scope of the mono-decarbonylation. A range
of functional groups were found to be compatible, including
methyl ether (2d), fluoride (2e), chloride (2f), bromide (2g),
and ester (2j) groups. Notable examples include the halides
(2e–g), which provide handles for further functionalization via
2 | J. Name., 2012, 00, 1-3
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Me
tBu
Ni(cod)2 (10 mol%)
IPrMe.HCl (20 mol%)
Cs2CO3 (20 mol%)
View Article Online
O
S
O
DOI: 10.1039/C8CC09352K
S
S
S
S
S
+
Ph
Ph
Ph
Ph
Ph
Ph
Ph
S
3a
3d
3g
3b
3e
77% (>20:1)
74% (>20:1)
(a)
3c
3f
3i
Ph
S
69% (>20:1)
O
1a
Dioxane
150 oC, 10 h
3a
2a
OMe
F
Cl
55% yield
35% yield
S
S
Ni(cod)2 (10 mol%)
PPh3 (20 mol%)
O
O
60% (10:1)
57% (>20:1)
Me
69% (>20:1)
+
Ph
Ph
Ph
(b)
(c)
S
Ph
S
O
1a
toluene
150 oC, 35 h
iPr
3a
Br
2a
60% yield
22% yield
S
S
S
O
3h
3k
65% (>20:1)
79% (>20:1)
69% (>20:1)
Conditions
Ph
Ph
Ph
S
Ph
S
MeOOC
MeO
MeO
MeO
2a
3a
S
S
S
52% yield in mono-decarbonylative conditions
3l
76% (>20:1)
60% (>20:1)
3j
71% (>20:1)
86% yield in double-decarbonylative conditions
Scheme 3. Control experiments
Based on these observations and literature reports,9 we
propose the possible mechanism shown in Scheme 4. The first
step is oxidative cleavage of the C(acyl)–S bond to form the
corresponding Ni(II) intermediate INT1. Subsequent
decarbonylation generates the corresponding intermediate
INT2. Reductive elimination from INT2 affords thioester 2a.
Under double-decarbonylative conditions, thioester 2a
undergoes C(acyl)−S activation to give intermediate INT3.
Subsequent decarbonylation and reductive elimination give
S
3m
77% (>20:1)
Standard conditions: 1 (0.2 mmol), Ni(cod)2 (10 mol%), IPrMe.HCl (20 mol%),
Cs2CO3 (20 mol%), toluene (2 mL), 150 °C, 22 h. Isolated yields. Double-
decarbonylation:mono-decarbonylation selectivities are given in parentheses.
a
b
c
Preliminary studies showed that mono-decarbonylation of
aryl–alkyl ketothioesters was also feasible (Scheme 2). The
reaction gave a low yield (34%) under mono-decarbonylative
conditions, but the product 2n was obtained in 74% yield with
Ni(PCy3)2Cl2 as the catalyst.9b However, under the standard
double-decarbonylative
ketothioester 1n only gave the mono-decarbonylated product
2n.
thioether 3a.
O
conditions,
the
aryl–alkyl
S
Ph
Ph
Ph
S
Ph
CO
O
O
1a
3a
[NiIIL] SPh
Ph [NiIIL] SPh
Ph
oxidative
addition
reductive
elimination
O
Ni(PCy3)2Cl2 (10 mol%)
O
INT4
Na2CO3 (1.5 equiv)
O
INT1
CO
S
Ph
Ph
S
dioxane
160oC, 15 h
O
[Ni0L]
double-decarbonylation
2n
(74%)
mono-decarbonylation
decarbonylation
1n
decarbonlyation
oxidative
CO
Scheme 2. Ni-catalyzed decarbonylation of aryl-alkyl ketothioester.
A series of control experiments were performed to investigate
the reaction pathway. The reaction of 1a was initially
conducted under double-decarbonylative conditions but with
a shorter reaction time; 3a (35%) and 2a (55%) were obtained
(Scheme 3a). As shown in Scheme 3b, the reaction of 1a
afforded 3a (22%) and 2a (60%) under mono-decarbonylative
conditions with a longer reaction time. This suggests that 2a
could be an intermediate in the double decarbonylation.
Thioester 2a was also used as the substrate under both sets of
conditions. The results show that thioester 2a was converted
to the desired product 3a in 86% yield under double-
decarbonylative conditions and in 52% yield under mono-
decarbonylative conditions (Scheme 3c).
reductive
elimination
addition
CO
[NiIIL] SPh
O
Ph
[NiIIL] SPh
Ph
Ph
SPh
2a
O
INT3
O
INT2
Scheme 4. Possible mechanism
Finally, to highlight the utility of this decarbonylation
reactions, sequential cross-couplings were investigated
(Scheme 5). The bromide moiety in 5 can serve as the first
reactive center in a Suzuki coupling to give biaryl 4o, and the
ketone can then provide a functional handle for the synthesis
of thioethers and thioesters.
O
O
O
S
1) SeO2, C5H5N
Pd(OAc)2/DABCO
Cs2CO3, DMF
Ph
Me
Me
O
2) NaOH, (COCl)2
PhSH, Et3N, CH2Cl2
Ph
Br
Ph
1o
( 64%)
5
4o
(90%)
Ni(cod)2 (10 mol%)
O
IPrMe.HCl (20 mol%)
Ni(cod)2 (10 mol%)
PPh3 (20 mol%)
O
Ph
Ph
Cs2CO3 (20 mol%)
S
S
Ph
Ph
O
S
Dioxane
150 oC, 22 h
Ph
toluene
150 oC, 15 h
Ph
3o
(67%)
2o
(84%)
1o
Scheme 5. Site-selective cross-coupling/decarbonylations.
In summary, an unusual reactivity of α-ketothioesters is
described. The use of different ligands enabled Ni-catalyzed
mono- and double-decarbonylative C−S bond formation to be
achieved in a controlled fashion. Compared with traditional
methods for C–S bond formation, the new protocols have the
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advantages of high atom efficiency, synthetic flexibility, and
use of inexpensive Ni catalysts. This decarbonylative strategy
therefore provides a viable alternative for the synthesis of
thioesters and thioethers.
We are grateful to the NSFC 21502149, the Education
Department of Shaanxi Provincial Government (2018JM2012)
for financial support and the Key Science and Technology
Innovation Team of Shaanxi Province (2017KCT-37).
Conflicts of interest
There are no conflicts to declare.
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DOI: 10.1039/C8CC09352K
O
Ni
O
Ni
SR
Ar SR
Ar
SR
Ar
O
IPrMe
mono
decarbonylation
PPh3
double
decarbonylation
A method for Ni-catalyzed controlled decarbonylation of α-ketothioesters via changing the
ligands was achieved