Direct Synthesis of Sulfinamides by the Copper-Catalyzed Electrophilic Amidation of Sulfenate Anions

Article abstract of DOI:10.1002/adsc.201701510

A method for the construction of sulfinamides via the copper-catalyzed electrophilic amination of sulfenate anions using N-benzoyloxyamines as the amination reagents. This procedure featured with the capture of in-situ generated sulfenate anions from β-sulfinyl esters under mild conditions, which provides an efficient strategy for the synthesis of diverse sulfinamides in moderate to good yields. (Figure presented.).

Full text of DOI:10.1002/adsc.201701510

Title: Direct Synthesis of Sulfinamides by the Copper-Catalyzed
Electrophilic Amidation of Sulfenate Anions
Authors: Junliang Zhang and Qiang Dai
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Advanced Synthesis & Catalysis
10.1002/adsc.201701510
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Direct Synthesis of Sulfinamides by the Copper-Catalyzed
Electrophilic Amidation of Sulfenate Anions
a
a
Qiang Dai and Junliang Zhang *
a
Shanghai Key Laboratory of Green Chemistry and Chemical Process, School of Chemistry and Molecular Engineering,
East China Normal University, 3663 N. Zhongshan Road, Shanghai 200062, China
Fax: (+86)-21–6223-5039; e-mail: jlzhang@chem.ecnu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Abstract: A method for the construction of sulfinamides via
the copper-catalyzed electrophilic amination of sulfenate
anions using N-benzoyloxyamines as the amination
reagents. This procedure featured with the capture of in-situ
generated sulfenate anions from β-sulfinyl esters under mild
conditions, which provides an efficient strategy for the
synthesis of diverse sulfinamides in moderate to good yields.
Keywords: sulfinamide; copper; electrophilic amidation;
sulfenate Anion; N-benzoyloxyamine
The
sulfinyl-derived
compounds,
especially
sulfinamides, are frequently found in many organic
molecules and play vital roles for applications in
organic chemistry, biological chemistry, and material
sciences.[ Furthermore, sulfinamides can also act as
N-sulfinyl protecting group for ease of removal under
1]
[2]
mild conditions. In addition, chiral sulfinamides are
[3]
widespreadly used in modern asymmetric chemistry.
The commonly procedures for the synthesis of
sulfinamides often require two or more synthetic steps
[4]
[5]
[6]
from sulfinic acids, sulfinates, sulfinyl chlorides,
[7]
disulfides, and homolytic substitution at the sulfur
atom.[ In recent years, new methodologies for the
synthesis of sulfinamides have emerged with the goal
of process simplification, using mild conditions, and
improving overall synthetic efficiency. Recently, Sun
developed an efficient pathway through direct
activation of tert-butyl sulfoxide by NBS under acidic
conditions and subsequent reaction with N-
8]
Scheme 1. Recent New Protocols for Synthesizing
Sulfinamides and sulfoxides.
[9]
nucleophiles to access sulfinamides (Scheme 1a).
Very recently, Shi also disclosed a nice cross-coupling
method for the synthesis of aryl sulfinamides using
arylboronic acids and DAST-type reagents as the
starting materials (Scheme 1b).[10] With the
significance of sulfinamides, there is considerable
demand in devising more mild, large scale, convenient
and efficient synthetic strategies to afford aryl and
alkyl sulfinamides and therefore increase the
exploration of sulfinamide chemistry.
Since Schwan’s summative work in sulfenate
[11]
anion, it’s great application prospect in biological
and synthetic chemistry has been realized and led to
[12]
many useful contributions in recent years.
The
burgeoning chemistry of these intermediates are
inseparable from the diversified sulfinyl precursors
and efficient and reliable approaches for their
[13-19]
generation,
such as (i) the retro-Michael reaction
1
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Advanced Synthesis & Catalysis
10.1002/adsc.201701510
of β-sulfinyl esters in the presence of base,[13,14] (ii)
envisaged that the electrophilic amidation of
nonstabilized sulfenate anions generated by β-sulfinyl
esters 2 might be feasible to construct sulfinamides via
the S−N bond formation (Scheme 1d).
[15]
fluoride triggered elimination of β-sulfinyl silanes,
(
iii) Mislow-Braverman-Evans rearrangement of
[16]
allylic sulfoxides,
(iv) the addition-elimination
[17]
process of aryl benzyl sulfoxides,
(v) thermal
fragmentation of tert-butyl sulfoxides,[18] and so on.
Despite a number of successful applications of
sulfenate anions have been reported, most of them are
Table 2. Exploration of Sulfenate Precursors Scope.a)
limited in the construction of S–C bond to prepare
sulfoxides.[
13-19]
Example of building S–X bonds is
rarely reported, especially S−N Bond. Once
groundbreaking work done by using β-sulfinyl esters 2
[
13]
in the PTC catalytic system
or Pd-mediated
process[ to achieving alkylation or arylation of
sulfenate anions certainly needs to keep pace with the
rapid development of synthetic methodology (Scheme
14]
1c).
Table 1. Optimization of Reaction Conditions.a)
Entry Catalyst
Base
T/
(oC) (%)
Yieldb)
1c)
2
Pd
(dba)
/xantphos
LiO Bu
t
80
80
0
25
2
3
t
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
2
2
2
/xantphos LiO Bu
a)
Reaction conditions: unless otherwise noted, all reactions
3
4
5
6
7
8
/xantphos KOH
80
80
80
80
80
trace
0
were carried out with 0.2 mmol of 1, 0.4 mmol of 2, 0.4
t
/xantphos NaO Bu
t
mmol of LiO Bu, 10 mol% of CuI and bpy, in toluene (2
/xantphos Cs
2
CO
3
0
o
mL) at 10 C under Ar for 5 h.
t
CuBr/xantphos
CuI/xantphos
LiO Bu
53
62
t
We initiated our research by using β-sulfinyl ester
a to generate the desired sulfenate anion and
LiO Bu
1
(CuOTf)
2
•Tol/
t
LiO Bu
80
34
combination with N-benzoyloxyamine 2a as nitrogen
electrophile. It was found that no desired product was
obtained under the Pd-catalysis (Table 1, entry 1). To
our satisfaction, the expected sulfinamide 3a was
xantphos
t
9
CuI/xantphos
CuI/dppbe
CuI/ phen
CuI/ bpy
CuI/ bpy
CuI/ bpy
CuI/ bpy
CuI/ bpy
CuI/ bpy
LiO Bu
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
10
0
trace
20
t
1
1
1
1
1
1
1
1
0
1
2
3d)
4e)
5f)
6f)
7f)
LiO Bu
isolated in 25% yield when using Cu(OAc) as catalyst
2
t
LiO Bu
62
t
and LiO Bu as base (Table 1, entry 2). It was identified
that the reaction is very sensitive to the base. Other
bases, such as NaO Bu, KO Bu, KOAc or Cs
t
LiO Bu
80
t
t
t
LiO Bu
64
2
CO did
3
t
not produce the desired sulfinamide (Table 1, entries 4
and 5, for details, see Table S1) and only a trace
amount of 3a was observed with the use of KOH
LiO Bu
75
t
LiO Bu
94
t
LiO Bu
96
(
Table 1, entry 3). A series of copper salts were found
t
LiO Bu
94
effective to proceed the desired transformation, with
CuI serving as the most effective catalyst in toluene at
a)
Reaction conditions: unless otherwise noted, all reactions
8
0 °C (Table 1, entries 6-8). When lowering the
were carried out with 0.2 mmol of 1a, 0.3 mmol of 2a, 0.4
mmol of base, 10 mol% of catalyst ([M] to Ligand = 1:1) in
indicated solvent (2 ml) and temperatures under Ar for 5 h.
temperature to r.t., xantphos and dppbe (1,2-
Bis(diphenylphosphanyl)benzene) all produced much
lower yields (Table 1, entries 9 and 10), while N-
ligands came to show higher efficiency than phosphine
ligands and CuI/bpy proved to be the most efficient
catalyst system (Table 1, entries 11 and 12). Among
the solvents tested, using toluene still performed the
highest yield (Table S1). The ratio of base and
substrates also had a great impact on the
transformation. Variation the amount of base
b)
c)
Isolated yield. 2 mol% Pd
2
t
(dba)
3
and 5 mol% xantphos
d)
e)
t
f)
were used. 0.3 mmol of LiO Bu. 0.5 mmol of LiO Bu.
0
.4
mmol
of
2a.
dppbe
=
1,2-
Bis(diphenylphosphanyl)benzene.
In light of recently developed copper-catalyzed
electrophilic amination in organic synthesis,
[
20]
we
2
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Advanced Synthesis & Catalysis
10.1002/adsc.201701510
decreased the yield of 3a. (Table 1, entries 13 and 14).
While increasing the dosage of the substrate 2a to 0.4
mmol was vital to improving 3a to 94% yield (Table 1,
entries 15). Finally, the highest yield (96%) was
We next explored the substrate scope of N-
benzoyloxyamines, as shown in Table 3. The first four
examples used simple acyclic amino electrophilic
reagents 2b−2e, and all of those gave moderate to good
results of the desired sulfinamides 3m−3p. It is
interesting to note that, when using pyrrole derived
amination reagent, an increase in the amount of base
was needed to promote the transformation of 1a
completely. Six- and seven-membered ring amination
reagents all readily participated in the reaction to
afford 3r, 3s and 3u−3w in good yields, except for 3t.
we assumed the more reactivity and instability of the
isoquinoline derived amination reagent led to the low
yield of 3t. Sulfinamide 3u was obtained in 89% yield
as a 1.4:1 mixture of diastereomeric isomers.
o
obtained when running the reaction at 10 C (Table 1,
entries 16 and 17). It should note that no electrophilic
amination at the oxygen (4) was observed in all the
reaction conditions, despite it may occur at either the
[
11, 12b]
sulfur or the oxygen according to earlier
and
[
21]
recent reports on hydroxysulfenylation reactions.
Table 3. Exploration of N-benzoyloxyamines Scope.a)
Gram scale synthesis of 3a and 3v were also
performed under the standard conditions with 96% and
9
4% yields respectively, without affecting the reaction
efficiency, thus demonstrating the good reliability of
the present reaction (Scheme 2).
Scheme 2. Gram-Scale Experiments. reaction conditions:
t
4
1
.5 mmol of 1a, 9.0 mmol of 2a or 2k, 9.0 mmol of LiO Bu,
o
0 mol% of CuI and bpy, in toluene (45 mL) at 10 C under
Ar for 5 h.
a)
Reaction conditions: unless otherwise noted, all reactions
were carried out with 0.2 mmol of 1a, 0.4 mmol of 2, 0.4
t
mmol of LiO Bu, 10 mol% of CuI and bpy, in toluene (2
To investigate whether the catalytic cycle involves
o
b)
t
mL) at 10 C under Ar for 5 h. 0.6 mmol of LiO Bu was
used.
an radical pathway, we conducted the reaction of 1a
and 2a in the presence of 2.0 equivalents of radical
scavenger TEMPO. The expected coupling product 3a
was still obtained in 73% yield efficiently with no
TEMPO-additive products detected, indicating that the
reaction may not procced via the radical pathway (eq
With the optimal conditions in hand, we first
surveyed the scope of the reaction by varying the
structure of β-sulfinyl ester 1 (Table 2). The efficient
formation of 3b−g illustrated that the corresponding
sulfenate anions were all released efficiently whether
electron-rich or electron-deficient substituents bearing
on the aryl ring. In addition, the steric effect did
interfere with the reaction efficiency. p- and m-tolyl
substituted sulfenates afforded the corresponding
sulfinamides 3c and 3d in 79% and 84% yields,
respectively, whereas o-tolyl sulfenate remarkably
diminished the yield to 46%. 2-Naphthyl sulfenate
precursor was also applicable to the present reaction,
providing the desired sulfinamide 3h with high
efficiency. Besides aromatic substrates, aliphatic
sulfenate precursors are also applicable to this reaction.
The linear and cyclic alkyl sulfenates were both
smoothly transformed into the corresponding products
1
).
Based on the above result and recent developments
copper-catalyzed umpolung electrophilic
in
[20]
aminations, a reasonable mechanistic pathway for
the copper-catalyzed electrophilic amination of
sulfenate anion is illustrated in Scheme 3. At first,
sulfenate anion B generated in situ from base mediated
retro-Michael reaction of β-sulfinyl esters 1 (see
scheme 1d). The ligand exchange of a Cu(I) complex
3
i−l in yields ranging from 47 to 82%.
3
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Advanced Synthesis & Catalysis
10.1002/adsc.201701510
t
t
Program of Eastern Scholar at Shanghai Institutions of Higher
Learning.
and LiO Bu to give Cu−O Bu complex C followed by
transmetalation with the sulfenate anion B furnishes
the sulfinyl copper intermediate D. An umpolung
electrophilic
amination
with
the
O-
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benzoylhydroxylamine 2 then occurs, forming the
desired sulfonamide product 3 and Cu−OBz complex
E. Finally, ligand exchange with LiO Bu regenerates
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We gratefully acknowledge the funding support of NSFC
(21425205, 21672067), 973 Program (2015CB856600), and the
4
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Advanced Synthesis & Catalysis
10.1002/adsc.201701510
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Advanced Synthesis & Catalysis
10.1002/adsc.201701510
COMMUNICATION
Direct Synthesis of Sulfinamides by the Copper-
Catalyzed Electrophilic Amidation of Sulfenate
Anions
Adv. Synth. Catal. Year, Volume, Page – Page
Qiang Dai, Junliang Zhang*
6
This article is protected by copyright. All rights reserved.