Cu-Catalyzed Desulfonylative Amination of Benzhydryl Sulfones

Article abstract of DOI:10.1002/chem.201805638

A new method for the synthesis of benzhydryl amines from the reaction of readily available sulfone derivatives with amines is described. The Cu-catalyzed desulfonylative amination not only provides structurally diverse benzhydryl amines in good yields, but is also applicable to iterative and intramolecular aminations. Control experiments suggested that the formation of a Cu-carbene intermediate generated from the sulfone substrate, which represents a new route for desulfonylative transformations.

Full text of DOI:10.1002/chem.201805638

A Journal of
Accepted Article
Title: Cu-Catalyzed Desulfonylative Amination of Benzhydryl Sulfones
Authors: Cathleen Marie Crudden, Masakazu Nambo, Yasuyo Tahara,
and Jacky C.-H. Yim
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To be cited as: Chem. Eur. J. 10.1002/chem.201805638
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Supported by

10.1002/chem.201805638
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COMMUNICATION
Cu-Catalyzed Desulfonylative Amination of Benzhydryl Sulfones
Masakazu Nambo,*[a] Yasuyo Tahara,[a,+] Jacky C.-H. Yim,[a,+] and Cathleen M. Crudden*[a,b]
Abstract: A new method for the synthesis of benzhydryl amines
from the reaction of readily available sulfone derivatives with amines
is described. The Cu-catalyzed desulfonylative amination not only
provides structurally diverse benzhydryl amines in good yields, but is
also applicable to iterative and intramolecular aminations. Control
experiments suggest the formation of a Cu-carbene intermediate
generated from the sulfone substrate, which represents a novel
route for desulfonylative transformations.
sulfonyl group can direct a-functionalization of simple and
readily available sulfone derivatives, permitting the facile
preparation of benzylic electrophiles without additional synthetic
steps. Activated sulfones bearing 3,5-bis(trifluoromethyl)phenyl
sulfones undergo mild desulfonylative cross-coupling reactions
to afford multiply-arylated methanes in minimal synthetic steps.
[12b] Herein we report the use of inexpensive Cu salts to catalyze
desulfonylative aminations yielding benzhydryl amine derivatives
in good to excellent yields. A variety of benzhydryl sulfones and
amines can be employed, and iterative and intramolecular
aminations rapidly afford valuable amine compounds. Control
experiments suggest the generation of an electrophilic Cu-
carbene as a key intermediate.
Methods for the construction of carbon–nitrogen bonds are
highly valuable in organic chemistry since amines are frequently
found in biologically active molecules.[1] Remarkable progress
has been made in the development of catalytic amination
reactions, providing useful synthetic strategies routes to complex
amine compounds from simple building blocks.[2] Among amine
derivatives, the benzhydryl amine is an attractive structural motif
that possesses unique biological activities.[3] However, synthetic
approaches to this class of molecules still rely heavily on
classical methods such as SN2 reactions on benzhydryl halides
with amines, which requires the preparation of relatively
unstable and toxic benzhydryl halides. Although reductive
amination of diarylketones[4] and nucleophilic addition of
organometallic reagents to aldimines[5] are potential alternatives,
these methods are not effective for secondary amines due to
slow formation of iminium intermediates.[6]
R1
R2
Previous Work
H
Pd cat.
Ar2X
N
Ar2
Ar1
R1
R2
OCO2R
Ar1
H N
nitrene
precursors
Ar2
Ar1
R1
N
R2
Ar2
H
Ar1
Pd, Cu
cat.
various
cat.
Ar2
NNHTs
R1
R2
Ar1
Ar2CHO
Ar1I
TMS N
Ni cat.
This Work: Cu-catalyzed desulfonylative amination
Ar2
R1
Ar2
R1
N
R2
Cu cat.
To address these challenges, new synthetic routes have
been developed using transition-metal catalyzed cross-
SO2ArF
H N
Ar1
R2
Ar1
LiOt-Bu
coupling[7,8]
,
reductive coupling[9], and C–H amination
diverse
benzhydryl amines
reactions[10] Recently, Doyle reported an elegant Ni-catalyzed
three-component coupling of benzaldehydes, arylhalides, and N-
silylamines to afford unsymmetric benzhydryl amines.[11] In this
communication, we describe new synthetic approach to these
important structures that does not require the use of any
sensitive reagents or the multistep preparation of the benzhydryl
precursors.
Ar2X
H
stable and readily available sulfone
primary and secondary amines
Cu-carbene intermediate
SO2ArF
Ar1
Pd cat.
Scheme 1. Synthesis of Benzhydryl Amine Derivatives by Transition Metal
Catalysis.
We began our investigation by studying the desulfonylative
amination of benzhydryl 3,5-bis(trifluoromethyl)phenyl sulfone 1a
with morpholine 2a as a model reaction (Table 1). In early
experiments using LiOt-Bu as a base, we found that Pd catalysts,
which were effective for desulfonylative cross-coupling reactions
in our previous studies[12a-c], did not give any amination product.
However, the use of 20 mol % CuCl as a catalyst gave the
amination product 3aa in 81% yield (entry 1). Other Cu(I) salts
and CuCl2 were found to be less reactive than CuCl (entries 2-5).
Additionally, the presence of common ligands such as 2,2’-
bipyridyl (bpy) and N-heterocyclic carbene (SIPr) inhibited
product formation (entries 6, 7). The effect of the counter cation
of the base was crucial: when NaOt-Bu and KOt-Bu were used
instead of LiOt-Bu, product yields were significantly decreased
(entries 8, 9).
Recently, we have developed cross-coupling reactions using
benzylic sulfone derivatives as a new class of electrophile in
which carbon–sulfonyl bond activation can be accomplished via
Pd and Ni catalysis.[12] One significant advantage of sulfone-
based electrophiles is that the strongly electron-withdrawing
[a]
Prof. Dr. M. Nambo, Y. Tahara, Dr. J. C.-H. Yim, Prof. Dr. C. M.
Crudden
Institute of Transformative Bio-Molecules (WPI-ITbM)
Nagoya University, Chikusa, Nagoya, 464-8602 (Japan)
E-mail: mnambo@itbm.nagoya-u.ac.jp
cruddenc@chem.queensu.ca
[b]
[+]
Prof. Dr. C. M. Crudden
Department of Chemistry
Queen's University, Chernoff Hall, Kingston, Ontario, K7L 3N6
(Canada)
These authors contributed equally to this work.
Settling on CuCl and LiOt-Bu, we were able to improve the
Supporting information for this article is given via a link at the end
of the document.
yield to 90% by conducting the reaction at
a higher
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10.1002/chem.201805638
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concentration (entry 10). Decreasing catalyst loading or lowering
the reaction temperature diminished the yield (entries 11, 12),
thus 20 mol % CuCl at 120 ºC was selected as our optimal
reaction conditions. Finally, benzhydryl phenyl sulfone showed
imine. Fortunately, we found that by substituting DPEphos as
the ligand and toluene as solvent we could suppress formation
of the undesired imine, improving the yield to 68% (See
Supporting Information).[9b] With regards to functional groups,
protected alcohol, chloro, acetal, and olefin moieties were found
to be compatible.
low
conversion
(entry
13),
indicating
that
3,5-
bis(trifluoromethyl)phenyl group functions is more reactive.
Table 1. Optimization of Cu-catalyzed desulfonylative amination of
diphenylmethyl sulfone 1a with morpholine 2a (ArF = 3,5-(CF3)2C6H3).[a]
Table 2. Scope of Cu-catalyzed desulfonylative amination of 1a with amine 2
(ArF = 3,5-(CF3)2C6H3).[a]
R1
R2
R1
R2
Ph
Ph
Ph
Ph
20 mol % CuCl
SO2ArF
Ph
Ph
Ph
Ph
Cu cat.
H N
N
SO2ArF
3 equiv LiOt-Bu
dioxane
120 ºC, 24 h
H N
2a
O
N
O
3 equiv Base
dioxane
120 ºC, 24 h
1a
2
3
1a
3aa
Ph
Ph
Ph
Ph
NMe
Ph
Ph
N
O
N
N
Cl
N
Entry
Cu cat.
Base
Yield [%][b]
Ph
Ph
3aa (89%)
3ab (85%)
3ac (79%)
3ad (59%)
1
CuCl
CuBr
CuI
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
NaOt-Bu
KOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
LiOt-Bu
81
2
73
Ph
N
Ph
O
O
Ph
Ph
Ph
Ph
3
27
N
N
O
4
CuOAc
CuCl2
72
O
OTBDPS
5
52
3ae (1.12 g, 92%)b
3af (71%)c
3ag (32%)
6
CuCl / bpy
Cu(SIPr)Cl
CuCl
33
Ph
Me
Ph
Ph
Bu
Ph
Me
Ph
Me
N
NEt2
N
7
18
N
N
Ph
Ph
Bu
Ph
Cy
Ph
8
8
3ah (71%)
3ai (69%)
Ph
3aj (29%d, 68%e) 3ak (trace)
9
CuCl
23
Ph
Ph
H
N
Ph
H
Ph
H
H
10[c]
11[c,e]
12[c,f]
13[c,g]
CuCl
90 (89)[d]
76
N
N
N
Ph
Ph
Cy
Ph
n-C10H23 Ph
Ph
CuCl
Me
3am (82%) 3an (55%d, 72%e) 3ao (70%)
3al (84%)
CuCl
62
Ph
Ph
H
N
Ph
H
O
H
N
Ph
Ph
CuCl
52
N
O
Ph
Ph
3ar (41%d, 68%f)
3aq (85%)
3ap (73%)
[a] Conditions: 1a (0.1 mmol), 2a (2.0 equiv), Cu catalyst (20 mol %), ligand
(20 mol %), base (3.0 equiv), dioxane (0.33 M). [b] Yields were determined by
GC using dodecane as an internal standard. [c] Concentration was 0.5 M. [d]
Isolated yield (0.2 mmol scale). [e] 10 mol % of CuCl was used. [f] Reaction
was conducted at 100 °C. [g] Benzhydryl phenyl sulfone was used instead of
1a.
[a] Conditions: 1a (0.2 mmol), 2 (2.0 equiv), CuCl (20 mol %), LiOt-Bu (3.0
equiv), dioxane (0.5 M), 120 ºC, 24 h. Isolated yield was given in parentheses.
[b] 2.4 mmol scale. [c] 1.2 equiv of amine was used. [d] Yields were
determined by GC using dodecane as an internal standard. [e] 3 equiv of
amine and 4 equiv of base were used. [f] DPEphos (20 mol %) and 4 equiv of
base were used and reaction was conducted in toluene (0.5 M).
With optimized reaction conditions in hand, the scope of
amines was investigated (Table 2). A variety of cyclic amines
(2a-e) were reacted to give the corresponding products in high
yields. Notably, compound 3ae could be produced on gram
scale in excellent yield. Carbazole 2f could also be coupled and
even aza-crown ether 2g afforded the amination product 3ag,
albeit in low yield. Acyclic secondary amines (2h-j) were also
reactive, however dibutylamine 2j required an excess of amine
and base, and the reaction with the more bulky N-
methylcyclohexylamine 2k did not afford the desired product.
Various sulfone derivatives were easily prepared via Pd-
catalyzed a-arylation, and were employed in amination reactions
with morpholine 2a (Table 3). Sulfones bearing electron-
donating (1b, 1c) and electron-withdrawing groups (1d, 1e) on
one of the arenes reacted with 2a to afford the corresponding
products in high yield. The bulky o-tolyl (1f) and 1-naphthyl (1g)
substituents and heteroaromatics such as 3-thienyl (1h) and 3-
pyridyl (1i) were well-tolerated. Interestingly, the dibenzosuberyl
group (1j), which is important pharmacophore in medicinal
chemistry, could be employed in this amination.
Primary amines (2l-q) could also be employed, but aniline 2r
gave a mixture of amination product 3ar and the corresponding
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Table 3. Scope of Cu-catalyzed desulfonylative amination of 1 with amine 2a
(ArF = 3,5-(CF3)2C6H3).[a]
a)
Ph
Ph
Ph
Ph
20 mol % CuCl
no
conv.
1a
3 equiv LiOt-Bu
dioxane
120 ºC, 4 h
3 equiv LiOt-Bu
dioxane
120 ºC, 4 h
(83% conv.)
Ar2
Ar1
Ar2
Ar1
20 mol % CuCl
4a
SO2ArF
N
O
H N
2a
O
66% yield
(GC)
3 equiv LiOt-Bu
dioxane
120 ºC, 24 h
1
3
b)
1a (1 equiv)
Ph
20 mol % CuCl
4a
R
3 equiv LiOt-Bu
dioxane
120 ºC, 24 h
(82% conv.)
Ph
p-Tol
R = p-Me, 3ba, (72%)
R = p-OMe, 3ca, (97%)
R = m-CF3, 3da, (87%)
R = p-F, 3ea, (82%)
p-TolCH2SO2Ph
5 (2 equiv)
6
N
O
34% yield
(GC)
11% yield
(GC)
N
O
R = o-Me, 3fa, (90%)
Scheme 2. Control experiments (ArF = 3,5-(CF3)2C6H3).[a]
3ga (82%)
Ar2
Ar1
R1
R2
Ar2
Ar1
S
1
N
Li
N
SO2ArF
CuLn
LiOt-Bu
3
t-BuOH
1’
N
O
N
O
N
O
LiOt-Bu
Ar2
Ar1
Ar1(Ar2)
Ar2(Ar1)
Li+
t-BuOH
Li+
Ar2
Ar2
Ar1
CuLn
NR1R2
CuLn
3ha (77%)
3ia (58%)
3ja (76%)
SO2ArF
[a] Conditions: 1a (0.1 mmol), 2 (2.0 equiv), CuCl (20 mol %), LiOt-Bu (3.0
Ar1
4
C
A
equiv), dioxane (0.5 M), 120 ºC, 24 h. Isolated yield was given in parentheses.
-CuLn
-LiSO2ArF
Ar2
Ar1
To gain insight into the Cu-catalyzed desulfonylative
amination, several control experiments were carried out. During
optimization of the reaction of 1a with 2a, we observed
tetraphenylethylene 4a as a by-product. In the absence of amine
2a, 4a was formed in 66% GC yield from 1a (Scheme 2a). In
addition, no conversion was observed with base alone,
suggesting that a Cu-stabilized carbene intermediate rather than
the free-carbene species would be generated from CuCl and a-
lithiated 1a. The Wang group reported the Cu-catalyzed
olefination of N-sulfonylhydrazones with sulfones, which is
proposed to proceed via Cu-carbene species.[13] From the
similarities with our reaction conditions, we hypothesized that a
similar olefination would occur if the Cu-carbene intermediate is
formed from sulfones instead of hydrazones. To examine this
hypothesis, we reacted sulfone 1a with p-tolylmethyl phenyl
sulfone 5 under our standard conditions (Scheme 2b). This
reaction proceeded to give the expected olefination product 6
along with 4a in 34% and 11% yields, respectively. As
dimerization of 5 did not occur, the reaction likely proceeds by
preferential generation of Cu- carbene species derived from 1a,
LiSO2ArF
CuLn
Ar1
LnCu
Ar2
HNR1R2 2
LiOt-Bu
Li+
SO2ArF
B
1’
Ar1 Ar2
Scheme 3. Proposed catalytic cycle.
Finally, we demonstrated the synthetic utility of this method
by employing the a-arylation of benzylsulfones for the concise
synthesis of complex amine derivatives (Scheme 4). Iterative
amination was carried out using p-benzoylbenzhydryl sulfone
derivative 1k, which was easily prepared by the Pd-catalyzed a-
arylation of benzyl sulfone 7 (Scheme 4A). Compound 1k could
be converted into 1l by classical methods without affecting the
sulfonyl group. Subsequently, a Cu-catalyzed desulfonylative
amination of 1l with 2b to give unsymmetric diamine 8.
Our method can also be employed in an intramolecular
sense, leading to the formation of cyclic amines (Scheme 4B).
Benzhydryl sulfone derivatives bearing an amino group with
different alkyl tether lengths (9m-o) by Pd-catalyzed a-arylation
of benzyl sulfone 7 with iodoarenes followed by transformation
of methoxymethoxy group to amino group. Under standard
conditions, compounds 9m-o were reacted to give various cyclic
amines, which were isolated as the corresponding N-tosylated
products (10m-o) in good yields. These results indicate that this
method can rapidly provide a variety of functionalized amines,
such as 8 and 10, which are difficult to synthesize by only typical
amination processes in short steps.
which then reacts with a-lithiated
desulfination yields 6 or 4a, respectively.
5 or 1a. Subsequent
The proposed catalytic cycle is shown in Scheme 3. Initially,
a-lithiated 1 reacts with the Cu catalyst to form species A, which
then undergoes desulfination to generate Cu-carbene
intermediate B. Subsequently, the attack of amine 2 on the
electrophilic carbene center of B forms C. Protonation of C gives
the amination product 3 and regenerates the Cu catalyst. As a
side reaction pathway, B can react with a-lithiated 1 followed by
desulfination to give the olefin 4.
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A. Iterative amination
O
B. Intramolecular
amination
n OMOM
(n= 1-3)
a.
f.
Br
H
Ph
I
SO2ArF
Pd(OAc)2/P(t-Bu)3
(87 %)
Pd(OAc)2/P(t-Bu)3
Ph
7
b. NaBH4
c. SOCl2
d. 2a
(ArF = 3,5-(CF3)2C6H3)
g. h. i.
n OMOM
SO2ArF
SO2ArF
O
(61-85%, 3 steps)
(74%, 3 steps)
O
Ph
Ph
Ph
n NH2
SO2ArF
9m (n=1)
9n (n=2)
9o (n=3)
1k
1m (n=1), 67%
1n (n=2), 57%
1o (n=3), 59%
Ph
SO2ArF
Ph
N
j. CuCl, k. TsCl
Ph
1l
O
e. 2b, CuCl
NTs
N
N
NTs
NTs
(83%)
Ph
10m (77%)
Ph
Ph
Ph
10n (78%)
Ph
10o (56%)
8
[2]
[3]
Reviews: a) I. P. Beletskaya, A. V. Cheprakov, Organometallics 2012,
31, 7753–7808. b) P. Ruiz-Castillo, Buchwald, S. L. Chem. Rev. 2016,
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Scheme 4. Synthetic Applications. Condition: (a) ArBr, Pd(OAc)2, P(t-Bu)3,
Cs2CO3, CPME, 125 ºC; (b) NaBH4, THF/MeOH, rt; (c) SOCl2, CH2Cl2, 50 ºC;
(d) 2a, MeCN, reflux; (e) 2b, CuCl, LiOt-Bu, dioxane, 120 ºC; (f) ArI, Pd(OAc)2,
P(t-Bu)3, Cs2CO3, CPME, 145 ºC; (g) HClaq, THF/MeOH, 70 ºC; (h)
phthalimide, PPh3, DIAD, THF/toluene, rt; (i) hydrazine, EtOH, 80 ºC; (j) CuCl,
LiOt-Bu, dioxane, 120 ºC; (k) TsCl, NaOH, CH2Cl2/H2O, rt.
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In summary, we have developed a new synthetic method for
the preparation of benzhydryl amines by
a Cu-catalyzed
desulfonylative amination. This strategy represents a novel,
modular route for the preparation of biologically active
benzhydryl amines. The possibility of generating a reactive Cu-
carbene species from stable and readily accessible sulfone
derivatives, leading to the exploration of new types of
desulfonylative reactions will provide new routes to a variety of
complex molecules. Mechanistic investigations and the
development of new transformations of organosulfones are
ongoing in our laboratory.
[4]
[5]
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[6]
[7]
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Acknowledgements
This work was supported by KAKENHI from JSPS (17K17805 to
M.N.). M.N. thanks the Ichihara International Scholarship
Foundation for financial support. JSPS and NU are
acknowledged for funding of this research through The World
Premier International Research Center Initiative (WPI) program.
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Conflict of Interest
[8]
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The authors declare no conflict of interest
Keywords: Desulfonylative Amination • Cu Catalysis • Sulfone •
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[1]
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10.1002/chem.201805638
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10.1002/chem.201805638
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
Author(s), Corresponding Author(s)*
R1
R2
Ar2
R1
R2
n
Page No. – Page No.
Ar2
via
SO2ArF
H N
N
Title
Ar1
Ar1
Ar2
Cu cat
CuL
Ar1
n
NH2
NH
F
Text for Table of Contents
Cu-carbene
intermediate
desulfonylative
amination
SO2Ar
Ar1
Ar1
(n=1-3)
This article is protected by copyright. All rights reserved.