Stereospecific Reactions of Donor–Acceptor Cyclopropanes with Thioketones: Access to Highly Substituted Tetrahydrothiophenes

Article abstract of DOI:10.1002/anie.201708346

Lewis-acid-catalyzed reactions of 2-substituted cyclopropane 1,1-dicarboxylates with thioketones are described. Highly substituted tetrahydrothiophenes with two adjacent quaternary carbon atoms were obtained in a stereospecific manner under mild conditions and in high yield when using AlCl₃ as Lewis acid. Moreover, an intramolecular approach was successfully implemented to gain access to sulfur-bridged [n.2.1] bicyclic ring systems. Conversion of selenoketones, the heavier analogues, under similar conditions resulted in the formation of various tetrahydroselenophenes.

Full text of DOI:10.1002/anie.201708346

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
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Accepted Article
Title: Stereospecific Reaction of Donor-Acceptor Cyclopropanes
with Thioketones: A Novel Access to Highly Substituted
Tetrahydrothiophenes
Authors: Daniel B. Werz, André Augustin, Peter G. Jones, and
Maximilian Sensse
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201708346
Angew. Chem. 10.1002/ange.201708346
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10.1002/anie.201708346
Angewandte Chemie International Edition
COMMUNICATION
Stereospecific Reaction of Donor-Acceptor Cyclopropanes with
Thioketones: A Novel Access to Highly Substituted
Tetrahydrothiophenes
André U. Augustin, Maximilian Sensse, Peter G. Jones, and Daniel B. Werz*
Dedicated to Professor Dr. Stefan Schulz on the occasion of his 60th birthday
Abstract: Lewis-acid-catalyzed reactions of 2-substituted cyclo-
propane 1,1-dicarboxylates with thioketones are described. Highly
substituted tetrahydrothiophenes with two adjacent quaternary carbon
atoms were obtained in a stereospecific manner under mild conditions
and in high yield using AlCl3 as Lewis acid. Moreover, an
intramolecular approach was successfully implemented to gain
access to sulfur-bridged [n.2.1] bicyclic ring systems. Conversion of
selenoketones, the heavier analogs, under similar conditions resulted
in the formation of various tetrahydroselenophenes.
accepting substituents.[10] This substitution pattern leads to an
easily cleavable bond. The emerging 1,3-zwitterionic interme-
diates are able to undergo various transformations such as
rearrangements,[11] ring-opening reactions with electrophilic and
nucleophilic components[12] or cycloaddition reactions.[13] One-,
two-, three- and four-atom components were successfully
inserted, leading to four-,five-, six- and seven-membered carbo-
and heterocyclic compounds via (3+n) annulation reactions.[11-13]
To afford substituted tetrahydrofurans, Johnson and Waser made
use of the dipolar CO double bond in aldehydes and ketones,[14,15]
whereas cyclopentane or cyclopentene derivatives were obtained
by inserting highly polarized CC double or triple bond
systems.[16,17] Whereas these types of annulations are well
established and even catalytic, enantioselective protocols have
been developed, higher homologs of ketones such as thio- and
The carbonyl group is probably one of the most abundant and
versatile functional groups in organic compounds. In contrast, its
heavier analogs, thio- and selenoketones, are much less
prominent. The carbon-sulfur π–bond shows a high reactivity
because of the poor orbital overlap between two elements that
differ significantly in size. On the one hand, this fact makes
thiones interesting reagents for organic chemists. On the other
hand, the handling of these compounds is challenging since they
tend to oligomerize and undergo various side reactions.
Presumably, the latter is one reason why their chemical value has
been underestimated in the past. Nevertheless, thiocarbonyls
have been employed for the construction of sulfur-containing
heterocycles.[1] Direct access to substituted thiiranes was realized
by a formal [2+1]-cycloaddition with carbenes,[2] whereas four-
membered thietanes were accessed from the corresponding
olefins,[3] allenes,[4] ketenes[5] or arynes[6] in a [2+2]-process
(Scheme 1). The hetero-Diels-Alder-reaction of thiocarbonyls with
dienes is well explored and various 2H-thiopyrans have been
selenoketones have never been subjected to
cycloaddition with D-A cyclopropanes.
a
[3+2]-
obtained.[7] Remarkably,
a five-membered ring-formation of
thioketones and a three-carbon unit has rarely been reported.[8]
Donor-acceptor (D-A) cyclopropanes are one of the most
frequently used three-atom building blocks.[9] Their special
reactivity is explained by the high ring strain of about 115 kJ/mol
and the vicinal arrangement of electron-donating and electron-
Scheme 1. [n+2]-Cycloaddition processes of thioketones with Cn units and our
present work using D-A cyclopropanes as three-membered building blocks.
[*]
M. Sc. A. U. Augustin, B. Sc. M. Sensse, Prof. Dr. D. B. Werz
Technische Universität Braunschweig
Institute of Organic Chemistry
Hagenring 30, 38106 Braunschweig (Germany)
E-mail: d.werz@tu-braunschweig.de
At the outset of our studies, we chose cyclopropane diester 1a
and thioketone 2a as model substrates to optimize the conditions
for the anticipated [3+2]-cycloaddition process. As a starting point,
the reaction was carried out in dichloromethane at 25 °C for
8 hours. Whereas most of the commonly used Lewis acids gave
only traces or at best small amounts of the desired product (Table
1, entries 1-3), AlCl3 instantly delivered 3a in moderate yield
(entry 4). Further optimization demonstrated that an increase of
the amount of thiobenzophenone 2a has a very beneficial effect
and resulted in quantitative product formation (entries 5-6).
Homepage: http://www.werzlab.de
Prof. Dr. P. G. Jones
Technische Universität Braunschweig
Institute of Inorganic and Analytical Chemistry
Hagenring 30, 38106 Braunschweig (Germany)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found:
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10.1002/anie.201708346
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COMMUNICATION
Table 1. Optimization of the reaction conditions.[a]
With the optimized conditions in hand, we examined the scope of
the reaction, first varying the donor (R1) at the D-A cyclopropane 1
(Scheme 2). Various aryl units bearing different electron-donating
and electron-withdrawing substituents (3b-3g and 3k) furnished
the desired products in up to 99% yield. Methyl substituents in
ortho-, meta- and para-position were also tolerated, as were bulky
groups such as naphthyl residues (3h-3j and 3l).
Besides aryl groups, weakly electron-donating aliphatic moieties
(e.g. cyclohexyl and vinyl residues) were successfully converted
into the corresponding THT scaffolds in good yields (3m-3n). The
transformation also proceeded smoothly with furyl and thienyl
donors (3o-3p). Decoration of the three-membered ring with
succinimide or phthalimide afforded the desired products 3q-3r in
moderate to good yields.
After these promising results, the generality of the protocol was
evaluated using different thiocarbonyls. To our satisfaction, other
aliphatic and aromatic thioketones and mixed derivatives
performed well under similar conditions. As depicted in Scheme 3,
the cycloaddition process worked well for the reaction with bulky
adamantanethione and cyclopropenethione to construct spiro
compounds 4a and 4b in up to 89% yield. Subsequently, a series
of non-symmetric thioketones was subjected to the reaction
conditions to afford both the cis- and trans-products in good yields
(4da-4ga). Initial attempts under the standard conditions gave
both diastereomers in a ratio of about 1:1. Lowering the reaction
temperature to 5 °C furnished the isomers in acceptable
diastereoselectivity of up to 4:1. NMR experiments by NOE
confirmed our expectations that the cis-product is favored.
Entry
1
2
3
4
5
6
7
8
LA
[mol%]
20
2a (eq.)
1.0
1.0
1.0
1.0
1.5
2.0
2.0
2.0
Solvent
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
THF
Yield [%]
traces
15
33
52
78
99
99
92
88
72
42
84
MgBr2
Sc(OTf)3
Yb(OTf)3
AlCl3
AlCl3
AlCl3
20
20
20
20
20
10
5
AlCl3
AlCl3
20
AlBr3
2.0
9
20
Al(OTf)3
AlCl3
AlCl3
2.0
2.0
2.0
2.0
10
11
12
13
20
20
20
dioxane
DCE
AlCl3
90
[a] Reaction conditions: 1a (100 µmol), 2a, solvent (2.0 mL), 25 °C, 8 h, Ar
atmosphere; yields represent isolated and purified products; DCE = 1,2-
dichloroethane.
Next, we decreased the catalyst loading to 10 mol% without loss
of product formation, even 5 mol% gave 3a in 92% yield (entries
7-8). However, the yields dropped significantly when using AlBr3
or Al(OTf)3 as Lewis acid (entries 9-10). Other solvents such as
ethers or DCE did not match the yields obtained in
dichloromethane (entries 11-13).
Scheme 3. AlCl3-Catalyzed insertion of various thioketones
2 in D-A
cyclopropane 1a. [a] Reaction conditions: 1a (200 µmol), 2 (400 µmol), AlCl3
(10 mol%), CH2Cl2 (4 mL), 25 °C, 4 h, Ar atmosphere; yields represent isolated
and purified products; [b] AlCl3 (20 mol%).
Next, we explored the stereospecificity of the [3+2]-cycloaddition
by using enantioenriched cyclopropane (S)-1a (95% ee); product
4da was formed in excellent yield with 92% ee (Scheme 4).
Inversion at C1 was observed and confirmed by X-ray structure
elucidation.[18] This fact strengthens the assumption that the initial
Scheme 2. AlCl3-Catalyzed insertion of thiobenzophenone 2a into various D-A
cyclopropanes 1 leading to tetrahydrothiophenes 3. [a] Reaction conditions: 1
(100 µmol), 2a (200 µmol), AlCl3 (10 mol%), CH2Cl2 (2 mL), 25 °C, 4 h, Ar
atmosphere; yields represent isolated and purified products; [b] AlCl3
(20 mol%); [c] 200 µmol scale.
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10.1002/anie.201708346
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COMMUNICATION
attack of the sulfur follows an SN2-type reaction pathway followed
by ring-closure.[14]
tetrahydroselenophenes 9a-9f were synthesized in moderate to
good yields.
Scheme 4. Stereospecificity experiment. [a] Only the major diastereomer
(R,R)- 4da is shown; (S,R)-4db shows similar results (see SI).
These results paved the way for an intramolecular variant,
resulting in bicyclic scaffolds via a simple one-pot process. Six
easily available model systems 5 were generated. In all of these
systems a D-A cyclopropane and a carbonyl unit (either an
aldehyde or a ketone) are tethered to each other (Scheme 5).
Lawesson’s reagent was utilized to convert the carbonyl into a
thiocarbonyl moiety. During this one-pot process bicyclic seven-
and eight-membered ring systems 7a-7f comprising one sulfur
bridge were formed in yields of 53-98%. In the formation of seven-
membered rings, the thiocarbonyl moieties immediately inserted
into the activated three-membered ring system affording
oligocyclic compounds of type 7. No additional Lewis acid was
required; Lawesson’s reagent seems to play a dual role, as both
thionation reagent and weak Lewis acid.[19] The sulfur-bridged
azepine 7c shows that even a thioaldehyde was able to undergo
this reaction in moderate yield.
Scheme 6. AlCl3-Catalyzed insertion of selenoketones into D-A-cyclopropanes.
[a] Reaction conditions: 1 (100 µmol), 8 (400 µmol), AlCl3 (10 mol%), benzene
(10 mL), 25 °C, up to 12 h; yields represent isolated and purified products.
In summary, we have developed a novel access to tetrahydro-
thiophene (THT) derivatives by
a
Lewis-acid-catalyzed
[3+2]-cycloaddition of thioketones and D-A cyclopropanes. A wide
range of highly substituted THT derivatives was obtained in a
stereospecific manner under mild conditions and high functional
group tolerance. An intramolecular variant paved the way to thia-
[n.2.1] bicyclic ring systems. The use of selenoketones, the
heavier analogs of thioketones, provided access to highly
substituted tetrahydroselenophenes.
Acknowledgments
This research was supported by the European Research Council
(ERC Consolidator Grant “GAINBYSTRAIN” to D.B.W.).
Keywords: cyclopropanes • donor-acceptor compounds •
thiocarbonyls • cycloaddition • bicyclic systems
Scheme 5. Intramolecular reaction leading to sulfur-bridged carbo- and
heterocyclic ring systems. [a] Reaction conditions: 5 (100 µmol), LR (150 µmol),
solvent (4 mL), 90 °C, up to 12 h; yields represent isolated and purified products.
[b] For stable thioketones: 6 (100 µmol), AlCl3 (20 mol%), CH2Cl2 (4 mL), 25 °C,
2 h; LR = Lawesson’s reagent.
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10.1002/anie.201708346
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Sheldrick, Acta Crystallogr. Sect. A 2008, 64, 112.
[22] The CIF files have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication no. CCDC-1568335 ((R)-3a),
-1568336 (3h), -1568337 (3i), -1568338 (3q), -1568339 (7b), -1568340
(7f) and -1568341 (9a). These data can be obtained free of charge from
The Cambridge Crystallographic Data Centre.
This article is protected by copyright. All rights reserved.

10.1002/anie.201708346
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
A. U. Augustin, M. Sensse, P. G. Jones,
D. B. Werz*
Page No. – Page No.
Stereospecific Reaction of Donor-
Acceptor Cyclopropanes with
Thioketones: A Novel Access to
Highly Substituted
Thiocarbonyl Insertion: Donor-Acceptor cyclopropanes undergo a formal [3+2]-
cycloaddition with thioketones using AlCl3 catalysis under mild conditions to yield
highly substituted tetrahydrothiophenes. Extension to an intramolecular variant led
to bicyclic products. Similar cycloadditions with bisarylselenoketones were also
achieved.
Tetrahydrothiophenes
This article is protected by copyright. All rights reserved.