Synthesis of γ-Keto Sulfones through a Three-Component Reaction of Cyclopropanols, DABCO ? (SO2)2 and Alkyl Halides

Article abstract of DOI:10.1002/adsc.202100066

A route to γ-keto sulfones through a metal-free reaction of cyclopropanols, DABCO ? (SO2)2 and alkyl halides is described. This reaction occurs under mild conditions in the absence of any catalysts, additives, or oxidants. Various functional groups including as ester, amino, methoxy, bromo, trifluoromethyl, nitro and carbonyl are tolerated well in this transformation, and the corresponding γ-keto sulfones are afforded in 35% to 95% yields. The proposed mechanism implies that this reaction proceeds through γ-keto sulfinate intermediate generated in situ, which further undergoes nucleophilic substitution with alkyl halides leading to γ-keto sulfones. (Figure presented.).

Full text of DOI:10.1002/adsc.202100066

UPDATES
DOI: 10.1002/adsc.202100066
Synthesis of γ-Keto Sulfones through a Three-Component
Reaction of Cyclopropanols, DABCO·(SO2)2 and Alkyl Halides
Chun Zhang,a Chao Zhang,b Jie Tang,a Shengqing Ye,b,* Mingliang Ma,a,* and
Jie Wub, c, d,
*
a
Shanghai Engineering Research Center of Molecular Therapeutics and New Drug Development, School of Chemistry and
Molecular Engineering, East China Normal University, Shanghai 200062, People’s Republic of China
E-mail: mlma@brain.ecnu.edu.cn
School of Pharmaceutical and Materials Engineering & Institute for Advanced Studies, Taizhou University, 1139 Shifu Avenue,
Taizhou 318000, People’s Republic of China
b
E-mail: shengqing.ye@tzc.edu.cn; jie_wu@fudan.edu.cn
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
345 Lingling Road, Shanghai 200032, People’s Republic of China
School of Chemistry and Chemical Engineering, Henan Normal University, 46 East Jianshe Road, Xinxiang 453007, People’s
Republic of China
c
d
Manuscript received: January 18, 2021; Revised manuscript received: April 5, 2021;
Version of record online: ■■■, ■■■■
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.202100066
of alkylsulfones is based on the oxidation of thioether[5]
Abstract: A route to γ-keto sulfones through a
metal-free reaction of cyclopropanols, DAB-
CO·(SO2)2 and alkyl halides is described. This
reaction occurs under mild conditions in the absence
or derivatization of alkyl sulfinate salts.[6] However,
these methods often suffer from strong oxidants, toxic
transition metal reagents and multiple steps, which
result in poor functional group tolerance towards the
of any catalysts, additives, or oxidants. Various
preparation of diverse alkylsulfones.
functional groups including as ester, amino, meth-
oxy, bromo, trifluoromethyl, nitro and carbonyl are
In the past decade, significant progress has been
witnessed in the preparation of sulfonyl compounds
tolerated well in this transformation, and the
via the insertion of sulfur dioxide. DABCO·(SO2)2
corresponding γ-keto sulfones are afforded in 35%
to 95% yields. The proposed mechanism implies
(1,4-diazabicyclo[2.2.2]octane-sulfur dioxide) and in-
organic sulfites are easy-handling and cheap sulfur
that this reaction proceeds through γ-keto sulfinate
dioxide surrogates, which have been broadly applied in
intermediate generated in situ, which further under-
sulfonylation reactions.[7–9] Recently, we reported the
goes nucleophilic substitution with alkyl halides
synthesis of alkylsulfones through the insertion of
leading to γ-keto sulfones.
sulfur dioxide with alkyl halides and organosilanes
promoted by transition metal salts.[10] However, an
equivalent amount of transition metal salt had to be
Keywords: Cyclopropanols; sulfur dioxide; three-
utilized and high reaction temperature was necessary
component reaction; sulfonylation
in the transformation. Therefore, developing mild and
environmentally friendly methods for the construction
of alkylsulfones is still highly desirable.
Due to the outstanding functionality in organic
Because of the strained cyclopropane ring, cyclo-
synthesis,[1] medicinal chemistry[2] and material propanols can undergo ring-opening reactions to afford
science,[3] sulfone motifs have attracted considerable alkyl substituted compounds. For instance, transition-
attention in past decades. As one of the most important metal catalyzed ring-opening reactions of cyclopropa-
sulfone motifs, alkylsulfones can be found broadly in nols would give rise to β-alkyl carbonyl compounds
pharmaceuticals and bioactive molecules frequently. via radical process.[11–12] In 2017, Kananovich and co-
For instance, alkylsulfone
A is an Alzheimer workers reported the synthesis of γ-keto sulfones via a
inhibitor,[4a] and alkylsulfone drugs have been used in copper-catalyzed oxidative sulfonylation reaction of
clinical for the treatment of parasitic, psoriasis and cyclopropanols (Scheme 1a).[6b] Additionally, Huang
herpes zoster (Figure 1).[4b–d] Traditionally, construction and co-workers discovered that cyclopropanols could
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bromide 2a as the model substrates. At the outset, this
model reaction was performed in DCE (1,2-dichloro-
°
ethane) at 40 C for 12 hours in the absence of any
metal-catalysts or additives (Table 1, entry 1). As
expected, the desired alkylsulfone 3aa was obtained in
50% yield. This result encouraged us for further
exploration. Solvent evaluation showed that the yield
of compound 3aa was decreased when the reaction
occurred in MeOH, MeCN, THF, 1,4-dioxane, or
DMSO (Table 1, entries 2–6). Compound 3aa could be
obtained in 68% yield when the amount of benzyl
bromide 2a was changed to 3.0 equivalent (Table 1,
entry 7). A better yield was observed when the reaction
time was extended to 24 hours (77%, Table 1, entry 8).
Gratifyingly, the desired product 3aa could be isolated
in 86% yield when the amount of DABCO·(SO2)2 was
further changed to 1.5 equivalent, and the reaction
time was extended to 36 hours (Table 1, entry 9). The
result could not be improved when the reaction
Figure 1. Alkylsulfone drugs and bioactive molecules.
°
temperature was changed to rt or 60 C (Table 1,
entries 10–11).
After obtaining the optimized conditions, the
substrate scope was then evaluated for this metal- and
oxidant-free reaction of cyclopropanols, DAB-
CO·(SO2)2 and alkyl halides. Initially, various alkyl
halides were explored in the reaction of cyclopropanol
1a and DABCO·(SO2)2. The result is shown in
Table 2. It was found that a broad range of alkyl
halides were compatible in this three-component
reaction. Reactions of benzyl bromides with both
Scheme 1. Synthesis of sulfones from cyclopropanols.
Table 1. Initial studies for the reaction of cyclopropanol 1a,
DABCO·(SO2)2 and benzyl bromide 2a.[a]
act as nucleophiles to react with electrophilic sulfo-
nium-type intermediates leading to β-arylated
ketones.[13]
On the other hand, sulfinates are synthetically
useful building blocks for the synthesis of sulfonyl
compounds.[14] Alkylsulfones could be easily prepared
through nucleophilic substitution of alkyl sulfinates
with alkyl halides under mild conditions. We recently
described that the combination of cyclopropanols with
sulfur dioxide would afford γ-keto sulfinate intermedi-
ates in situ, which would further react with electron-
deficient olefins leading to γ-keto sulfones
(Scheme 1b).[15] As our continuous interest in the
construction of sulfonyl compounds, we hypothesized
that alkyl sulfinate intermediates, generated in situ
from the reaction of cyclopropanols with sulfur
dioxide, would go through nucleophilic substitution
with alkyl halides to produce alkylsulfones. Herein, we
present an efficient route to γ-keto sulfones through a
three-component reaction of cyclopropanols, DAB-
CO·(SO2)2 and alkyl halides under mild conditions
(Scheme 1c).
Yield (%)[b]
°
Entry
Solvent
t (h)
T ( C)
1
2
3
4
5
6
DCE
MeOH
MeCN
THF
1,4-dioxane
DMSO
DCE
DCE
DCE
DCE
DCE
12
12
12
12
12
12
12
24
36
36
36
40
40
40
40
40
40
40
40
40
rt
50
15
27
37
28
3
68
77
86
82
75
7[c]
8[c]
9[d]
10[d]
11[d]
60
[a] Reaction conditions: DABCO.(SO2)2 (0.2 mmol), 1-naphthyl-
cyclopropanol 1 a (0.2 mmol), benzyl bromide 2 a
(0.4 mmol), solvent (2.0 mL), N2.
[b] Isolated yield based on 1-naphthylcyclopropanol 1a.
[c] Benzyl bromide (0.6 mmol) was used.
[d] DABCO.(SO2)2 (0.3 mmol) and benzyl bromide (0.6 mmol)
were used.
We started our initial evaluation by using naph-
thylcyclopropanol 1a, DABCO·(SO2)2 and benzyl
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compounds were explored in this reaction subse-
quently. Both α-bromo ketone 2u and α-bromo ester
2v were workable, leading to the corresponding
products 3au and 3av in 91% and 95% yields,
respectively. Moreover, allyl bromide 2w was a good
partner as well in this transformation, and product 3aw
was obtained in 62% yield. Notably, reactions using
alkyl iodides, such as methyl iodide and butyl iodide
could achieve the desired products 3ax and 3ay in
35% and 52% yields, respectively.
Table 2. Metal- and oxidant-free reaction of cyclopropanol 1a,
DABCO·(SO2)2 and alkyl halides 2.[a]
Subsequently, various functionalized cyclopropa-
nols were examined in this transformation. The results
are presented in Table 3. It was showed that 1-phenyl-
cyclopropanols bearing diverse functional groups in-
cluding fluoro, bromo and methoxyl on the aromatic
ring exhibited good reactivity (3ba–3ea). 1-Thiophen-
yl substituted cyclopropanol was workable as well in
this reaction, giving rise to the corresponding product
3fa in 69% yield. Moreover, alkyl-substituted cyclo-
propanols were applicable, leading to the desired
alkylsulfones in 63–81% yields (3ga–3ma). Reactions
of cyclopropanols with substitutions of olefin, cyclo-
propyl, chloroalkyl, and 3-bromo cyclobutyl were then
explored, and the corresponding products 3ja, 3ka,
Table 3. Reaction of cyclopropanols 1, DABCO·(SO2)2 and
benzyl bromide 2a.[a]
[a] Isolated yield based on cyclopropanol 1a.
[b] Alkyl iodides were used.
electron-donating and electron-withdrawing groups
substituted on the aromatic ring proceeded well under
the standard conditions, affording the corresponding
alkylsulfones in good to excellent yields (compounds
3aa–3an). Product 3aa was obtained in 60% yield
when benzyl chloride was employed in this reaction as
a replacement of benzyl bromide. Reaction of secon-
dary alkyl bromide also worked well, giving rise to the
corresponding product 3ao in 75% yield. Heterocy-
clic-substituted alkyl bromides were found to be
compatible in this transformation, and the expected
products were generated in 53–92% yields (3ap–3at).
Other type of alkyl halides, such as α-bromo carbonyl
[a] Isolated yield based on cyclopropanol 1.
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3la, and 3ma were generated as expected. However, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) or
no reaction occurred when 2-ethyl-1-(naphthalen-2-yl) BHT (2,6-di-tert-butyl-4-methylphenol), reaction of
cyclopropan-1-ol was employed as the substrate in this naphthylcyclopropanol 1a, DABCO·(SO2)2 and benzyl
reaction. Instead, the starting material of compound 1n bromide 2a afforded the corresponding product 3aa in
was recovered.
28% or 88% yield, respectively (Scheme 3, eqn a).
The synthetic utility of this reaction was then HRMS data indicated that TEMPO acted as an oxidant
investigated, and further modifications of alkylsulfone in this transformation which oxidized γ-keto sulfinate
3aa were performed. For example, reaction of com- to γ-keto sulfonate, resulting in the formation of
pound 3aa with NaBH4 afforded γ-hydroxyl sulfone 4 compound 3aa in low yield (See Supporting Informa-
in 98% yield (Scheme 2, eqn 1). Treatment of tion). Furthermore, a stepwise reaction was carried out.
compound 3aa with LiAlH4 provided alkylsulfone 5 in The outcome showed that γ-keto sulfinate intermediate
70% yield (Scheme 2, eqn 2). Vinyl sulfone 6 was was generated in situ during the reaction process (as
generated in 59% yield when compound 3aa reacted detected by HRMS. See Supporting Information),
with formaldehyde (Scheme 2, eqn 3). Moreover, a which could be further trapped by benzyl bromide 2a
gram-scale reaction of cyclopropanol 1a, DAB- giving rise to the desired product 3aa in 62% yield
CO·(SO2)2 and benzyl bromide 2a was carried out, (Scheme 3, eqn b). These results indicated that this
giving rise to product 3aa in 79% yield (Scheme 2, transformation might not be a radical process. How-
eqn 4).
ever, the pathway for the ring opening of cyclo-
Next, with our interest in the mechanism under- propanol with DABCO·(SO2)2 leading to γ-keto
standing, several control experiments were performed sulfinate is currently unclear, but most likely undergoes
(Scheme 3). With the addition of 3.0 equivalent of heterolytic cleavage.
On the basis of previous report[15] and the mecha-
nistic investigation shown in Scheme 3, a plausible
reaction pathway was then proposed (Scheme 4). We
reasoned that the combination cyclopropanol 1 with
DABCO·(SO2)2 would result in the formation of γ-
keto sulfinate B. This γ-keto sulfinate would further
undergo nucleophilic substitution with alkyl halides 2
to produce the corresponding product 3.
In summary, we have described a metal- and
oxidant-free reaction of cyclopropanols, DAB-
CO·(SO2)2, and alkyl halides under mild conditions.
Diverse γ-keto sulfones are generated, and various
types of alkyl halides are tolerated well in this
transformation. A plausible mechanism is proposed,
implying that during the reaction process, ring opening
of cyclopropanol with DABCO·(SO2)2 might undergo
heterolytic cleavage, and γ-keto sulfinate intermediate
generated in situ is the key intermediate. Followed by
nucleophilic substitution with alkyl halides, the corre-
Scheme 2. Transformations of alkylsulfone 3aa and gram-scale
reaction of cyclopropanol 1a, DABCO·(SO2)2 and benzyl
bromide 2a.
sponding γ-keto sulfones can be achieved efficiently.
Experimental Section
General experimental procedure for the reaction of
cyclopropanols 1, (DABCO)·(SO2)2, and Alkyl hal-
ides 2
Alkyl halide 2 (0.6 mmol) was added to a mixture of cyclo-
propanol 1 (0.2 mmol) and DABCO·(SO2)2 (0.3 mmol) in DCE
Scheme 3. Control experiments.
Scheme 4. Plausible mechanism.
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°
(2.0 mL) under N2 atmosphere. The mixture was stirred at 40 C
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solvent was evaporated and the residue was purified directly by
flash column chromatography (CH2Cl2/MeOH (v/v): 300/1 to
150/1) to give the corresponding product 3.
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Acknowledgements
Financial support from National Natural Science Foundation of
China (Nos. 21901178), the Leading Innovative and Entrepre-
neur Team Introduction Program of Zhejiang (No.
2019R01005), and the Open Research Fund of School of
Chemistry and Chemical Engineering, Henan Normal Univer-
sity (2020ZD04) is gratefully acknowledged. We thank Prof.
Pornchai Rojsitthisak in Chulalongkorn University for English
review.
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Synthesis of γ-Keto Sulfones through a Three-Component
Reaction of Cyclopropanols, DABCO·(SO2)2 and Alkyl
Halides
Adv. Synth. Catal. 2021, 363, 1–7
C. Zhang, C. Zhang, J. Tang, S. Ye*, M. Ma*, J. Wu*