Efficient Synthesis of γ-Lactones by Cobalt-Catalyzed Carbonylative Ring Expansion of Oxetanes under Syngas Atmosphere

Article abstract of DOI:10.1002/cctc.202001294

A practical route from oxetane or thietane to γ-(thio)butyrolactone via solvated-proton-assisted cobalt-catalyzed carbonylative ring expansion under syngas atmosphere has been established. A wide variety of γ-(thio)butyrolactones can be afforded in good to excellent yields. The versatility of this method has been well demonstrated in the synthesis of intermediates towards the natural product Arctigenin as well as the pharmaceuticals Baclofen and Montelukast. The observed promoting effect of glycol ether solvent has been rationally interpreted.

Full text of DOI:10.1002/cctc.202001294

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: Efficient Synthesis of γ-Lactones by Cobalt-Catalyzed
Carbonylative Ring Expansion of Oxetanes under Syngas
Atmosphere
Authors: Kaiwu Dong, Yitian Tang, Chaoren Shen, Qiyi Yao, Xinxin
Tian, and Bo Wang
This manuscript has been accepted after peer review and appears as an
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To be cited as: ChemCatChem 10.1002/cctc.202001294
Link to VoR: https://doi.org/10.1002/cctc.202001294
01/2020

10.1002/cctc.202001294
ChemCatChem
COMMUNICATION
Efficient Synthesis of γ-Lactones by Cobalt-Catalyzed Carbonyla-
tive Ring Expansion of Oxetanes under Syngas Atmosphere
Yitian Tang[a], Chaoren Shen[a], Qiyi Yao[a], Xinxin Tian[b], Bo Wang[c] and Kaiwu Dong*[a]
[a]
[b]
[c]
Dr. Yitian Tang, Dr. Chaoren Shen, M. Sc. Qiyi Yao, Prof. Dr. Kaiwu Dong
Chang-Kung Chuang Institute, and Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular
Engineering, East China Normal University, Shanghai 200062, PR China.
Prof. Dr. Xinxin Tian
Institute of Molecular Science, Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Shanxi University, Taiyuan 030006 PR
China
Dr. Bo Wang
Shanghai Puyi Chemical Co., Ltd., Shanghai 201612, PR China
Supporting information for this article is given via a link at the end of the document.
Abstract:
A
practical route from oxetane or thietane to γ-
salophen ligand had to be introduced into the cobalt-aluminium
catalyst system and only one unsubstituted oxetane was probed.
Thus, simpler and more practical catalyst system was yet to be
achieved.
(thio)butyrolactone via solvated-proton-assisted cobalt-catalyzed
carbonylative ring expansion under syngas atmosphere has been
established. A wide variety of γ-(thio)butyrolactones can be afforded
in good to excellent yield. The versatility of this method has been
well demonstrated in the synthesis of intermediates for natural
product Arctigenin and pharmaceuticals Baclofen and Montelukast.
The observed promoting effect of glycol ether solvent has been
rationally interpreted.
Activating the four-membered ring is the crucial precondition
for the carbonylative ring expansion of oxetane. Besides the
coordination with Lewis-acid catalysts, protonating oxetane by
strong Brønsted acid is the other potential but long-time
overlooked solution to implement the effective activation of
oxetane substrate. More than being able to catalyse
carbonylative reaction, HCo(CO)4 also possesses the aqueous
Brønsted acidity that comparable to hydrogen chloride.[12a]
Herein, we elaborated a facile protocol for the carbonylative
conversion of oxetane and thietane to γ-(thio)lactone by making
full use of the dual function of in-situ generated HCo(CO)4
catalyst. Its application in the synthesis of natural product and
pharmaceutical compounds was demonstrated. Significant
solvent effect on the reactivity of oxetane carbonylative ring
expansion was observed and rationalized.
The γ-lactone frameworks, in particular 4-substituted γ-lactones,
are versatile skeletons and building blocks for pharmaceuticals,
fine chemicals, and polymeric materials.[1] These γ-lactones can
also be important intermediates to prepare γ-amino acid, which
are ubiquitous in pharmaceutically active molecules.[2]
Comparing with those conventional accesses to γ-lactone, such
as Baeyer-Villiger oxidation of cyclobutanones,[3] nucleophilic
addition of organometallic reagent to 2,5-dihydrofuranone[4] and
reduction of 2,5-dihydrofuranone,[5] transition-metal-catalyzed
carbonylative ring expansion of oxetane, as
straightforward path, has the merits of quantitative atom
economy, broader functional-group tolerance, easier
a
more
accessibility of substrate as well as avoiding the usage of
stoichiometric additives. Oxetanes are readily available through
ring closing of 1,3-diols or Paternꢀ-Bꢁchi reaction between olefin
and carbonyl compound.[6] Therefore, we envisioned that
carbonylative ring expansion of oxetane by cobalt carbonyl
catalyst, as a practical waste- and noble-metal-free protocol,
would be a potent alternative to the above-mentioned routes
(Scheme 1).
In contrast to the well-established transition metal-catalyzed
carbonylative ring expansion of epoxides[7] or aziridines[8] as well
as its asymmetric catalysis variant[9] mainly based on the
corporation between Lewis acid and cobalt carbonyl complexes,
carbonylative ring expansion of oxetane was far less developed
(Scheme 1) and more challenging due to the lower reactivity of
four-membered ring than three-membered ring from ring-strain
relief (inherent ring strain: 106 kJ·mol−1 for oxetane, 112
kJ·mol−1 for epoxides).[6] Until now, regarding carbonylative ring
expansion of oxetane, only two cases respectively exploiting
cobalt-ruthenium[10] and cobalt-aluminium binary catalyst
systems were described (Scheme 1).[11] High pressure and
temperature were indispensable to the cobalt-ruthenium catalyst
system. For fabricating coordinative Lewis-acid catalyst, delicate
Scheme 1. Carbonylative ring expansion of strained small rings.
1
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Initially, 3-phenyloxetane (1a) and Co2(CO)8 were employed
as the model substrate and the pre-catalyst for condition
optimization (Table 1). Considering that HCo(CO)4 can be
afforded from the hydrogenolysis of Co2(CO)8 and inspired by
the previous report about the stochiometric reaction of oxetane
with HCo(CO)4 and carbon monoxide to give γ-hydroxy cobalt
acyl complex,[12] we investigated the reaction under syngas
atmosphere without any additives. Gratifyingly, β-phenyl-γ-
butyrolactone (2a) was obtained in good yield (entry 1). In
contrary, replacing syngas with carbon monoxide completely
suppressed the conversion of oxetane (entry 2). Using reductive
boron-, aluminum- or phenylsilyl hydrides instead of H2 led to the
undesired ring-opening reduction of oxetane and no target
product was detected (entry 3). These patterns indicated the
indispensability of hydrogen gas to the formation of HCo(CO)4.
Phosphine ligands were utilized to afford the less-acidic
phosphine-substituted cobalt carbonyl hydride complexes
HCo(CO)3L (L = phosphine ligand).[12a] Basic N-heteroaromatic
compounds were utilized to facilitate Co2(CO)8 disproportion to
Co(I) or Co(II) Lewis acid (e.g. [Co(CO)4(py)]+ and [Co(py)6]2+)
and carbonylation catalyst [Co(CO)4]- [13] or employed to promote
product yield in cobalt-catalyzed carbonylation of epoxides.[14]
Adding these phosphine ligands or N-heteroaromatic
compounds had little further improvement on the yield of 2a
(entries 4-7). Fewer product was formed when Co2(CO)8 was
substituted with cobalt(II) salts (Table 1, entries 8-10). Other
group VIII metal carbonyl clusters were also attempted to
replace Co2(CO)8, but none of them had satisfying catalytic
activity under syngas atmosphere (entries 11-13). It is
noteworthy that [(salph)Al(THF)2][Co(CO)4] catalyst developed
by Coates[11a] fails to exhibit any catalytic activity for this
substituted oxetane substrate in such conditions (entry 14) or
conditions reported by Coates[11a] (entry 15). This pattern implies
that the combination of Lewis acid and carbonylation catalyst is
not suitable for the carbonylative ring expansion of oxetanes.
When reducing reaction temperature to 60 oC, the yield of 2a
dropped to only 34% (entry 16).
10
11
12
13
14
15
Co(OAc)2 instead of Co2(CO)8
13
0
Ru3(CO)12 instead of Co2(CO)8
Fe2(CO)9 instead of Co2(CO)8
0
Mn2(CO)10 instead of Co2(CO)8
0
[(salph)Al(THF)2][Co(CO)4] (2 mol%) instead of Co2(CO)8
[(salph)Al(THF)2][Co(CO)4] (2 mol%) instead of Co2(CO)8
0[c]
0[d]
16
Performed at 60 oC
34
Reaction conditions: 1a (0.4 mmol), Co2(CO)8 (0.01 mol), DME (1 mL), 100 oC,
16 h. Conversions and yields were determined by GC. DME=
dimethoxyethane; DPPE
tetrahydrofuran [a] yield of isolated 2a. [b] 30 atm syngas (CO : H2 = 1: 1). [c]
30 atm CO. [d] Using the conditions of ref. 11a (toluene, 15 atm CO, 80 oC, 24
h).
=
1,2-bis(diphenylphosphino)ethane; THF
=
With the optimized reaction conditions in hand, the substrate
diversity of this carbonylative ring expansion protocol was
surveyed (Table 2). This method is applicable to various 3-
substituted oxetanes and is also suitable for 2-substituted
oxetane. Oxetanes possessing substituted aryl and benzyl
groups at 3-position can be well tolerated (2a-n). Among these
carbonylative expansion products, 2e and 2n are the key
intermediates in the synthesis of pharmaceutical Baclofen[15] and
natural product Arctigenin.[16] Oxetanes with mono-alkyl
substituents or di-substituents at 3-position can be converted to
corresponding β-substituted γ-butyrolactones in good yields (2o-
q). This carbonylative reaction proceeded smoothly in the ring
expansion of spiro-oxetane substrates to spiro-γ-butyrolactone
(2r and 2s). Strained cyclopropane ring remains intact in the
reaction conditions. Oxetane bearing functional group, such as
benzyloxy, phenoxy, thienyl, thioether and amide, gave the γ-
butyrolactone products in good to excellent yields (2t-z). More
impressively, the alkenyl group survived under the reductive
syngas atmosphere and the desired γ-butyrolactone 2aa was
obtained in 88% yield. Moreover, the remarkable versatility of
this carbonylative ring expansion reaction is reflected on the
conversion of thietane (2ab and 2ac) and 2-substituted oxetane
(2ad). Thietane is even less strained than oxetane (inherent ring
strain: 80.3 kJ/mol for thietane).[17] By highly correlated wave
function based ab initio method,[18] we evaluated the free-energy
changes (ΔG) of carbonylative ring expansion of oxetane and
thietane with CO to generate γ-butyrolactone and γ-
thiobutyrolactone. It shows that ΔG of γ-thiobutyrolactone is less
exothermic than γ-butyrolactone by about 13 kcal/mol (details
see Table S1 of SI). These figures imply that the carbonylative
ring-expansion of thietane is more arduous. By elevating the
loading of cobalt carbonyl catalyst and conducting the reaction
at elevated temperature, the transformation from thietane to γ-
thiobutyrolactone was also accomplished in fair to good yield
(2ab and 2ac). This simple approach avoids the usage of both
costly platinum Lewis acid and bidentate phosphine ligand in the
carbonylative ring expansion of thietane,[19] and it still remains
comparable catalytic effect. For 2-phenethyloxetane (2ad), the
carbonyl group was inserted exclusively from the less steric-
hindered side. In the carbonylative ring expansion of estrone-
attached 3-hydroxymethyl-3-methyloxetane, the ketone moiety
of estrone fragment was unaffected in syngas atmosphere and
89% product yield was attained (2ae). One important
Table 1. Comparison of reaction conditions
entry
Deviation from standard conditions
None
Yield (%)
1
2
3
4
5
6
7
8
9
85 (82)[a]
CO (30 bar) instead of syngas
NaBH4, LiAlH4 or PhSiH4 (10 mol%) instead of H2
Adding PPh3 (10 mol%)
0
0
0[b]
0[b]
12[b]
75[b]
0
Adding DPPE (5 mol%)
Adding 3-hydroxypyridine (10 mol%)
Adding pyrazole (10 mol%)
CoCl2 instead of Co2(CO)8
Co(acac)2 instead of Co2(CO)8
0
2
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10.1002/cctc.202001294
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COMMUNICATION
comparison should be underlined that by employing the cobalt-
aluminium binary catalyst [(salph)Al(THF)2][Co(CO)4] and the
reaction conditions reported by Coates and co-workers, neither
the conversion of substrates 1e, 1s and 1ac nor the
corresponding carbonylative ring expansion products 2e, 2s and
2ac was observed or obtained.
Table 2. Carbonylative ring expansion of various oxetanes and thietanes by
in-situ generated HCo(CO)4.
Scheme 2. Large-scale preparation of the key building block for Montelukast.
During the course of investigating substrate scope, we
noticed that diglyme, the DME-analogue solvent with higher
boiling point, was also suitable solvent for the carbonylative ring
expansion. This phenomenon drew out interest to probe the role
of solvent in this reaction. Once HCo(CO)4 is in-situ formed
through the hydrogenolysis of Co2(CO)8 under syngas
atmosphere,[12] its dissociation to active carbonylation catalyst
[Co(CO)4]- and solvated proton as well as the subsequent ion
complexing between oxetane substrate and solvated proton are
key to the carbonylative conversion of oxetane. Following this
deduction, the correlation between solvent and reactivity was
assessed by using 1a as the model oxetane substrate (Table 3).
Within expectation, DME-analogue solvent diglyme can also be
the effective solvent to achieve the full conversion of substrate
and good chemoselectivity (entry 2). Opposite to the results of
these two solvents, no conversion of 1a was detected in other
common monoether solvents (entries 3-6) or non-polar
hydrocarbon solvents (entries 7 and 8). In methanol, undesired
MeOH-involved ring-opening methoxylation and MeOH-initiated
oligomerization products instead of carbonylative ring-expansion
product was generated (entry 9). This series of results indicates
that the carbonylative ring-expansion reactivity of oxetane is
evidently dependent on solvent. Since DME and diglyme retain
higher hydrogen-bond basicity (i.e. Abraham basicity)[23] than
other ether solvents, we rationally conjecture that glycol-ether-
solvated proton, as the Brønsted acid species to activate
oxetane substrate, is crucial to gain the good reactivity. As a sort
of cyclic glycol ether, crown ether was reported to own the
capacity of binding proton.[24] To verify our conjecture, one
equivalent 12-crown-4 or 18-crown-6 was added into 1,4-
dioxane, one of the poor ether-type solvents for this ring-
expansion reaction. Indeed, adding crown ether into 1,4-dioxane
solvent boosts the carbonylative conversion of oxetane to γ-
lactone (entry 10 and 11).
Unless otherwise noted, reaction conditions were as follows: 1 (0.4 mmol),
Co2(CO)8 (0.01 mmol), DME (1 mL), syngas (30 atm, CO : H2 = 1 : 1), 100 oC,
16 h. The isolated yields of product 2. [b] [(salph)Al(THF)2][Co(CO)4] (0.01
mmol), CO (30 atm), toluene (1 mL), 80 oC, 16 h. [c] Co2(CO)8 (0.02 mmol). [d]
Co2(CO)8 (0.04 mmol). [e] Co2(CO)8 (0.02 mmol), diglyme instead of DME,
140 oC. [f] Co2(CO)8 (0.08 mmol), 120 oC
Table 3. Investigation of solvent effect.
To further manifest the practicality of this protocol,
carbonylative synthesis of 2s was carried out on the multigram
scale in the presence of 1 mol% Co2(CO)8 (Scheme 2). The
resulting γ-lactone was produced in 82% yield. This γ-lactone
can be further converted to (1-(mercaptomethyl)cyclopropyl)
acetic acid, one of the building blocks for synthesizing asthma
treatment medicine Montelukast.[20,21] In comparison to the
registered patents,[20b,22] our developed carbonylative method
provides a more straightforward and atom-economic route to the
building block for the synthesis of Montelukast.
entry
solvent (hydrogen-bond basicity)[a]
DME (0.68)
conversion (%)
yield (%)
85 (82)
82
1
2
3
>99
>99
0
diglyme (1.17)
THF (0.48)
0
3
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10.1002/cctc.202001294
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COMMUNICATION
Conflict of interest
4
5
2-methyl-THF (0.53)
dioxane (0.64)
MTBE (0.55)
0
0
0
0
The authors declare no conflict of interest.
6
0
0
Keywords: carbonylation • ring expansion • γ-butyrolactone •
oxetane • solvent effect
7
hexane (0)
0
0
8
toluene (0.14)
MeOH (0.47)
dioxane (0.64)
dioxane (0.64)
0
0
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Simple but useful: Solvated-proton-assisted cobalt-catalyzed carbonylative ring expansion of oxetanes or thietanes to γ-
(thio)butyrolactones under syngas atmosphere has demonstrated its versatility in the synthesis of intermediates for pharmaceuticals
and natural product. Glycol ether solvent plays an essential role in promoting the carbonylative conversion of the substrates.
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