Rare-Earth-Catalyzed Transsulfinamidation of Sulfinamides with Amines

Article abstract of DOI:10.1021/acs.orglett.1c01106

A rare-earth-catalyzed transsulfinamidation of primary sulfinamides with alkyl, aryl, and heterocyclic amines for the synthesis of diverse secondary and tertiary sulfinamides has been realized. Unlike transition metal-catalyzed cross-coupling approaches restricted to non-commercially available disubstituted O-benzoyl hydroxylamines, this newly developed protocol is suitable for diverse readily available primary and secondary amines without any modifications. Excellent catalytic activity and selectivity are achieved with Eu(OTf)3 under mild reaction conditions, which extends the applicability of rare-earth catalysis.

Full text of DOI:10.1021/acs.orglett.1c01106

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Letter
Rare-Earth-Catalyzed Transsulfinamidation of Sulfinamides with
Amines
Daheng Wen, Qingshu Zheng, Chaoyu Wang, and Tao Tu*
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ABSTRACT: A rare-earth-catalyzed transsulfinamidation of primary sulfina-
mides with alkyl, aryl, and heterocyclic amines for the synthesis of diverse
secondary and tertiary sulfinamides has been realized. Unlike transition metal-
catalyzed cross-coupling approaches restricted to non-commercially available
disubstituted O-benzoyl hydroxylamines, this newly developed protocol is
suitable for diverse readily available primary and secondary amines without any
modifications. Excellent catalytic activity and selectivity are achieved with
Eu(OTf)3 under mild reaction conditions, which extends the applicability of rare-earth catalysis.
ransamidation represents one of the most highly valuable
reactions for synthesis of diverse amides.1 Unlike the
significant advances achieved in the transamidation of amides,
to the best of our knowledge, the direct transformation of
sulfonamides or sulfinamides has not been reported (Scheme
1a). Sulfonamides and sulfinamides are widely found in
produce diverse functional sulfonamides by using O-benzoyl
hydroxylamines (OBzs) as amino sources.7 Subsequently,
Bolm and co-workers realized the first example of copper-
catalyzed transsulfinamidation of nucleophilic primary sulfina-
mides with air-sensitive triphenylphosphine as a ligand at 20
mol % catalyst loading (Scheme 1a).8 In both reactions, the
commercially unavailable and atom un-economic amino
reagents OBzs have to be used, which hampered the
practicability and applicability of the protocols. Furthermore,
the OBzs have to be disubstituted to increase their stability,
restricted to the formation of mainly tertiary sulfinamides.
Therefore, efficient transsulfinamidation of sulfinamides with
readily available amines to yield not only tertiary but also
secondary sulfinamides is highly desirable.
T
Scheme 1. Represented Synthetic Approaches for
Sulfinamides and Sulfonamides
However, the direct transamidation of sulfinamides with
amines is still unknown because both substrates are
nucleophilic.9 In light of the good performance of metal
Lewis acids, especially lanthanides salts, in the catalytic
transformation of amines with alkenes, alkynes, and cyanides,10
we conceived that the possible four-member-ring intermediate
mediated by Lewis acid may also aid the direct transamidation
of sulfinamides (Scheme 1b). The four-member-ring species
may not only activate both substrates simultaneously but also
accelerate the nucleophilic transformation.11 With this
hypothesis in mind, herein we realize a rare-earth-catalyzed
transamidation of primary sulfinamides to secondary and
tertiary sulfinamides by direct reaction with diverse alkyl, aryl,
and heterocyclic amines under mild reaction conditions
bioactive, pharmaceutical, and polymeric molecules.2 For
example, sulfinamides are considered as one of the most
widespread and privileged ligands,3 easily deprotectable N-
sulfinyl protecting groups, as well as precursors of sulfona-
mides.4 Conventional approaches5 for syntheses of sulfina-
mides often include multistep homolytic substitution of sulfinic
acids, sulfonates, sulfinyl chlorides, and disulfides. Various
efforts have thus been devoted to developing practical,
straightforward, and one-step approaches for syntheses of
sulfinamides and their derivatives.6
Received: March 31, 2021
Published: April 21, 2021
We have recently reported the first convenient copper-
catalyzed electrophilic amination of sodium sulfinates to
https://doi.org/10.1021/acs.orglett.1c01106
© 2021 American Chemical Society
Org. Lett. 2021, 23, 3718−3723
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a
(Scheme 1b). Unlike unsatisfactory outcomes in the Lewis
acid-accelerated equilibrium transamidation of amides with
amines,12 up to quantitative yields were achieved in our newly
developed europium-catalyzed transsulfinamidation.
Scheme 2. Substrate Scope of Various Primary Amines
Initially, 4-tolylsulfinamide (1a) and benzylamine (2a) were
selected to test our hypothesis with several Lewis acids (Table
1). The desired secondary sulfinamide 4 was obtained in 39%
a
Table 1. Optimization of the Reaction Conditions
b
entry
catalyst
yield (%)
1
2
3
4
5
6
7
8
CoCl2·6H2O
Ni(OAc)2·4H2O
CuCl2
39
trace
36
9
47
88
91
87
91
97
88
89
8
Zn(OAc)2
HAuCl4·6H2O
Sc(OTf)3
La(OTf)3
Ce(OTf)3
Nd(OTf)3
Eu(OTf)3
Tb(OTf)3
Yb(OTf)3
−
9
10
11
12
13
a
Under a N2 atmosphere, a catalyst (10 mol %), 4-tolylsulfinamide 1a
(0.5 mmol), and benzylamine 2a (0.55 mmol) were stirred in 2 mL of
b
MeCN at 50 °C for 24 h. Isolated yield.
yield with 10 mol % CoCl2·6H2O in acetonitrile at 50 °C for
24 h (Table 1, entry 1). When other Lewis acids were involved,
chloroauric acid showed the best catalytic activity (entries 2−
5). Considering the strong acidity of lanthanide salts and their
excellent performance in many reactions,13 a number of
lanthanide triflates were also applied (entries 6−12). To our
delight, excellent yields (87−97%) were obtained. Among
these, europium triflate displayed the best activity (97%, entry
10). As a comparison, in the case without any catalyst, <10% of
yields were obtained (entry 13). The solvent effect was also
investigated (Table S1), and acetonitrile was found to be the
best choice. Further optimization with a decrease in temper-
ature or the catalyst loading all led to inferior yields.
a
The reaction was carried out with 4-tolylsulfinamide 1a (0.5 mmol),
primary amines 2 (0.55 mmol), and Eu(OTf)3 (10 mol %) in 2.0 mL
b
of MeCN under a N2 atmosphere at 50 °C for 24 h. Isolated yields.
c
d
e
f
At 100 °C. With 20 mol % Eu(OTf)3. With 4 equiv of 2. With 4-
tolylsulfinamide 1a (1.1 mmol) and ethylenediamine (0.5 mmol).
With the optimal reaction conditions in hand, the feasibility
of the newly developed protocol was then investigated
(Scheme 2). The position of the methyl group on benzylamine
has almost no influence on the transformation (83−85%, 5a−
5c). Electron-rich or electron-deficient benzylamines all led to
the formation of corresponding sulfinamides 6a−7c in very
good yields (83−89%), including benzylamines with methoxy,
cyano, trifluoromethoxy, or halogen substituents. The amines
with bulky naphthalene or adamantane rings could also be
converted into corresponding sulfinamides in good yields (82−
84%, 8 and 9). All selected heterocyclic benzylamines also
resulted in excellent yields (≤99%, 10−11), even on a gram
scale (Scheme S1). In addition to phenethylamines, the
primary amines with longer alkyl chains were all compatible
with the protocol (69−94%, 12a−14b). Remarkably, primary
amines containing sensitive functional groups gave good yields,
as well (56−75%, 15−17). For instance, the selected
aminoalcohol, ethanolamine, with a global annual demand of
2 million tons,14 resulted in product 15 in a yield of 75%. The
alkyl diamine was also successfully converted to disulfinamide
18 under the standard reaction conditions.
Aromatic amines, which are less nucleophilic, were also
involved in this transsulfinamidation, though the yields were
slightly lower (19a−21). The selectivity of the substrates with
different types of amino groups was then investigated. The
aliphatic amino was much more reactive than the aromatic
amine, and product 22 with an unchanged aromatic amino
group was produced in a very good yield (84%). The reaction
with chiral substrates was also investigated, and a mixture of
diastereomers (dr 67:33) 23 was formed when using (S)-4-
tolylsulfinamide and (S)-1-phenylethylamine as reactants. Such
results may be helpful for the further understanding of the
plausible mechanism.
We further paid our attention to the feasibility of secondary
amines (Scheme 3). The acyclic secondary amines were all
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a
excellent yields (75−93%, 34−37). Secondary diamine was
also tolerated (65%, 38). A derivative of desloratadine, which
was a new antihistamine showing anti-inflammatory properties
in vitro,16 could also be obtained via our strategy (92%, 39).
These results clearly demonstrated the versatility and
applicability of our newly developed protocol.
Scheme 3. Substrate Scope of Various Secondary Amines
After investigation of the scope of amines, a series of
sulfinamides were subsequently selected as reaction partners
(Scheme 4). The electron-rich substrates were quite
a
Scheme 4. Substrate Scope of Diverse Sulfinamides
a
With sulfinamide 1 (0.5 mmol), primary amines 2a (0.55 mmol),
and Eu(OTf)3 (10 mol %) in 2.0 mL of MeCN under a N2
b
c
d
atmosphere at 50 °C for 24 h. Isolated yields. At 100 °C. With
a
With 4-tolylsulfinamide 1a (0.5 mmol), secondary amines 3 (0.55
20 mol % Eu(OTf)3 at 140 °C.
mmol), and Eu(OTf)3 (10 mol %) in 2.0 mL of MeCN under a N2
b
c
d
atmosphere at 50 °C for 24 h. Isolated yields. At 100 °C. With 20
e
mol % Eu(OTf)3 and 4 equiv of 3. With 0.275 mmol of
compatible, and good to excellent yields were found (90%−
91%, 40 and 41), whereas the electron-deficient sulfinamides
were slightly less active (58−77%, 42−45). Our protocol was
also compatible with sulfinamides even with bulky, hetero-
cyclic, and alkyl groups (≤99% yield, 46−51). Among them,
tert-butyl sulfinamide derivatives, which are widely used in
organic synthesis and chiral catalysis,17 could be prepared by
this strategy (62%, 48).
To explore the plausible mechanism, several control
experiments were performed. With the addition of a drop of
mercury or 1.5 equiv of 2,2,6,6-tetramethylpiperidinooxy
(TEMPO) to the reaction mixture, no obvious impact on
the transformation was observed (Scheme 5a), excluding
nanoparticles catalyzed and free radical reaction pathways.18
f
+
Me2NH2 Me2NCOO− salt as an amino source. With 4-tolylsulfina-
mide 1a (1.1 mmol) and piperazine (0.5 mmol).
compatible and readily converted into the corresponding
sulfinamides 24−27 in moderate to excellent yields (52−92%).
Due to the low boiling point of dimethylamine, dimethylam-
15
monium dimethylcarbamate (Me2NH2 Me2NCOO−) was
used instead, leading to a 52% yield for product 26a.
Secondary aryl amines were also suitable for this trans-
formation (62%, 27). Sensitive functional groups were well
tolerated. When N-allylmethylamine and diallylamine were
involved, the corresponding products 28a and 28b were
produced in good yields (73% and 77%, respectively), in which
the allylic moieties were untouched. When a substituted amino
alcohol was applied, moderate yield was attained (60%, 29)
without the generation of sulfonimidamides or esterification
products.
+
1
To understand the role of europium, H NMR studies were
performed (Scheme 5b). After the addition of europium triflate
to the CDCl3 solution mixture containing 4-tolylsulfinamide
(1a) or morpholine (3a), obvious changes of chemical shifts
were found in both cases, indicating both partners could
coordinate with europium. However, in a CDCl3 solution
containing both 1a and 3a, after the addition of Eu(OTf)3, the
signals for 3a were shifted downfield much more obviously
than those for 1a, suggesting the ability of 3a to coordinate to
the Eu center was stronger than that of 1a.
In addition to the acyclic amines, cyclic secondary amines
were also compatible. The ring size of amines slightly affected
the catalytic efficiency (63−76%, 30a−30c). Amines derived
from tetrahydroisoquinoline, morphiline, and piperazine
delivered the corresponding sulfinamides in good to excellent
yields (88−95%, 31−33). Piperazines with an amide groups
and trifluoromethyl, pyridine, piperonyl, and bis(4-
fluorophenyl)methyl substituents resulted in moderate to
The irritating gas ammonia was released, and a small amount
of white precipitate was also observed during the reaction. 19F
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Scheme 5. Control Experiments
Scheme 6. Proposed Mechanism
chelated four-member-ring intermediate has been proposed,
which extends the applicability of rare-earth catalysis.
a
Control experiment with a drop of mercury or 1.5 equiv of TEMPO
b
under standard conditions. 1H NMR spectra for (1) 1a and 3a, (2)
1a or 3a with Eu(OTf)3 (10 mol %) in 2.0 mL of MeCN under a N2
atmosphere at 50 °C for 1 h, (3) 1a, 3a, and Eu(OTf)3 (10 mol %) in
2.0 mL of MeCN under a N2 atmosphere at 50 °C for 1 h, or (4)
ASSOCIATED CONTENT
■
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* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.1c01106.
c
product 32. With (S)-1a (0.5 mmol) and (S)-2b (0.55 mmol) as
reactants under standard conditions.
Instrumentation and chemicals, optimization of reaction
condition, detailed mechanistic studies, and character-
ization data for products (PDF)
NMR spectra (Figures S1 and S2) revealed the white solid
might be generated ammonium triflate. To verify the possible
four-member-ring species generated during the transsulfinami-
dation, a control experiment involving chiral substrates was
also carried out (Scheme 5c). If the four-member ring was
involved, the products of two different configurations could be
obtained because the attack from both sides of SO was
possible; otherwise, chiral products with retained configuration
would be generated. The control experiment using sulfinamide
(S)-1a and amines (S)-2b as reactants resulted in a mixture of
diastereomers in a yield of 71%, confirming the formation of
possible four-member-ring species.
On the basis of our results, and combined with previously
reported mechanistic studies on lanthanide catalysis and
transamidation of amides,19 a plausible mechanism is proposed
(Scheme 6). Initially, Lewis acid Eu(OTf)3 coordinates with
amine to generate species A along with the formaiton of
ammonium salts. Then sulfinamide and species A form the key
four-member-ring intermediate C. Further isomerization yields
another crucial four-membered-ring intermediate D. Subse-
quent ring opening (E) and ligand exchange with amine led to
the formation of the desired product and ammonia along with
the regeneration of active catalytic species A.
In summary, a direct transsulfinamidation of sulfinamides
with various readily available amines was realized for the first
time by using europium triflate as a catalyst under mild
reaction conditions. Unlike previous studies on the transition
metal-catalyzed cross-coupling approaches with disubstituted
O-benzoyl hydroxylamines, this newly developed protocol is
quite compatible with a broad range of alkyl, aryl, and
heterocylic primary and secondary amines directly, generating
diverse secondary and tertiary sulfinamides in good to excellent
yields. A plausible mechanism involving a key europium-
AUTHOR INFORMATION
■
Corresponding Author
Tao Tu − Shanghai Key Laboratory of Molecular Catalysis
and Innovative Materials, Department of Chemistry, Fudan
University, Shanghai 200438, China; State Key Laboratory
of Organometallic Chemistry, Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences, Shanghai 200032,
China; Green Catalysis Center and College of Chemistry,
Zhengzhou University, Zhengzhou 450001, China;
orcid.org/0000-0003-3420-7889; Email: taotu@
fudan.edu.cn
Authors
Daheng Wen − Shanghai Key Laboratory of Molecular
Catalysis and Innovative Materials, Department of
Chemistry, Fudan University, Shanghai 200438, China
Qingshu Zheng − Shanghai Key Laboratory of Molecular
Catalysis and Innovative Materials, Department of
Chemistry, Fudan University, Shanghai 200438, China
Chaoyu Wang − Shanghai Key Laboratory of Molecular
Catalysis and Innovative Materials, Department of
Chemistry, Fudan University, Shanghai 200438, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.1c01106
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
■
Financial support from the National Key R&D Program of
China (2016YFA0202902), the National Natural Science
Foundation of China (21871059 and 21861132002), and the
Department of Chemistry at Fudan University is gratefully
acknowledged.
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