Palladium-Catalyzed Enantioselective Alkenylation of Sulfenate Anions

Article abstract of DOI:10.1021/acs.orglett.8b03943

A novel approach to synthesize enantio-enriched alkenyl/aryl sulfoxides is achieved by using CsF to generate sulfenate anions and conducting the catalytic enantioselective alkenylation with [Pd(allyl)Cl]₂/(2R)-1-[(1R)-1-[bis(1,1-dimethylethyl)phosphino]ethyl]-2-(diphenylphosphino)ferrocene (SL-J002-1). A wide variety of sulfoxides bearing sensitive functional groups are produced with high yields (up to 94%) and enantioselectivities (up to 92%).

Full text of DOI:10.1021/acs.orglett.8b03943

Letter
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
pubs.acs.org/OrgLett
Palladium-Catalyzed Enantioselective Alkenylation of Sulfenate
Anions
†
†
†,‡
and Patrick J. Walsh*,†
Chen Wu, Simon Berritt, Xiaoxia Liang,
†Roy and Diana Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia,
Pennsylvania 19104-6323, United States
‡
Natural Medicine Research Center, College of Veterinary Medicine, Sichuan Agricultural University, Chengdu 611130, People’s
Republic of China
*
S Supporting Information
ABSTRACT: A novel approach to synthesize enantio-
enriched alkenyl/aryl sulfoxides is achieved by using CsF to
generate sulfenate anions and conducting the catalytic
enantioselective alkenylation with [Pd(allyl)Cl] /(2R)-1-
2
[
(
(1R)-1-[bis(1,1-dimethylethyl)phosphino]ethyl]-2-
diphenylphosphino)ferrocene (SL-J002-1). A wide variety of
sulfoxides bearing sensitive functional groups are produced with high yields (up to 94%) and enantioselectivities (up to 92%).
nantioenriched sulfoxides are key structural motifs in
medicinal chemistry that are present in a broad range of
Another approach to enantio-enriched sulfoxides utilized the
−
14
E
generation of sulfenate anions (R−SO ) in transition-metal-
1
2
15
natural products, bioactive compounds, and marketed
catalyzed cross-coupling reactions. The first examples were
3
15a
drugs. Recently, they have also attracted attention as ligands
reported by Poli and Madec in 2007 (Scheme 1c). The
4
and been successfully applied in asymmetric catalysis. Vinyl
potential utility of this work was diminished by the limited
sulfoxides are particularly useful, because they can be
substrate scope and modest enantioselectivities (40%−80%).
5
16
electrophilic or nucleophilic at the α-position and are
We recently developed a method to generate sulfenate
6
electrophilic at the β-position. The synthetic utility of
anions from benzyl sulfoxides with yields as high as 95% and
enantioselectivities up to 94% (Scheme 1d). This system was
limited to the preparation of enantio-enriched diaryl sulfoxides
7
sulfoxides is demonstrated by their use as oxosulfonium ylides
and in Pummerer-type reactions.
8
t
Traditionally, enantioenriched sulfoxides are synthesized in
two ways: nucleophilic substitution with chiral sulfinyl amides
or esters, and catalytic enantioselective oxidation of sulfides.
that were stable to the basic conditions (NaO Bu). An
accompanying computational study highlighted the importance
of isomerization between O- and S-bound palladium sulfenate
9
17
The well-known Andersen procedure utilizes optically pure
anions in the enantio-determining step. Very recently, Zhang
menthyl p-tolylsulfinates, which require several recrystalliza-
tions to achieve enantiopurity. Organometallic reagents,
including organolithium and Grignard reagents, are required
in this procedure. These reagents may racemize the sulfoxide
designed a new chiral ligand for the arylation of a variety of
sulfenate anions in high yields (45%−96%) and very high
enantioselectivities (86%−99%), again using only aryl electro-
philes (Scheme 1e). Herein, we report a very mild palladium-
catalyzed coupling of sulfenate anions with both alkenyl and
aryl bromides to afford enantioenriched sulfoxides (Scheme
1f), expanding the scope of chiral sulfoxides accessible using
enantioselective coupling reactions.
10
stereocenter and limit the substrate scope. The most popular
enantioselective sulfide oxidation protocol was pioneered by
11
Kagan and Modena. This approach gives poor results when
the substituents on the sulfur are similar in size. Chemo-
selectivity can also be poor if over-oxidation to the sulfone
We recently reported the formation of racemic diaryl and
aryl alkyl sulfoxides in excellent yields from 2-(trimethylsilyl)-
1
1c
occurs.
A novel method to synthesize enantioenriched sulfoxides
ethyl substituted sulfoxides via a palladium-catalyzed cross-
12
15g,h
was developed by Dong and Houk. They utilized dynamic
kinetic resolution (DKR) of allylic sulfoxides relying on a
Mislow−Evans rearrangement coupled with a catalytic
asymmetric hydrogenation (Scheme 1a). Subsequently, a
hydrogenative kinetic resolution of vinyl sulfoxides using a
Rh/phosphine-phosphite complex as a catalyst was demon-
coupling reaction
(Scheme 2). The advantage of this
t
process is that CsF is a milder base than NaO Bu. Therefore,
we envisioned that these mild conditions would be more
suitable to an efficient asymmetric protocol and enable us to
expand the substrate scope of sulfenate anions in enantiose-
lective reactions with vinyl halides.
13
strated by Vidal-Ferran (Scheme 1b). Both methods give
high enantioselectivities to afford specific types of chiral
sulfoxides (n-propyl sulfoxides or ethyl sulfoxides).
Received: December 10, 2018
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.8b03943
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Scheme 1. Methods To Synthesize Chiral Sulfoxides
all the ligands screened, SL-J002-1 was the most promising. in
terms of yield and enantioselectivity (Table 1). It was then
used on a larger scale using 0.1 mL of 0.5 M solvent, providing
1
7
9% assay yield (AY, determined by H NMR integration with
CH Br as the internal standard) and moderate enantiose-
2
2
lectivity (71%, Table 1, entry 1, ee determined by chiral phase
SFC; see the Supporting Information). A survey of palladium
sources and solvents showed that [Pd(allyl)Cl] in THF gave
2
slightly higher yields with up to 79% ee (Table 1, entries 2 and
3
°
8
). When the reaction temperature was decreased to 50 and 40
C, the yield was maintained (85%−87%) and ee increased to
4% and 89%, respectively (Table 1, entries 4 and 5).
However, at 27 °C, the yield fell to 10% with 93% ee (Table 1,
entry 6). We found that changing the concentration did not
improve the yield or ee (Table 1, entries 7 and 8). Therefore,
our optimized conditions for the palladium-catalyzed enantio-
selective vinylation of sulfenate anions employ 2.5 mol %
[
Pd(allyl)Cl] with 5 mol % SL-J002-1 as the catalyst, 1a (0.5
2
mmol), 2a (1.0 mmol) and CsF (1.5 mmol) in 1 mL THF at
4
0 °C for 24 h (Table 1, entry 5).
With the optimized conditions in hand, a variety of sulfenate
anions were generated from aryl 2-(trimethylsilyl)ethyl
sulfoxides in the presence of vinyl bromide 2a (Scheme 3).
2
-(Trimethylsilyl)ethyl sulfoxides bearing electronegative or
electron-withdrawing groups, such as 4-F, 4-Cl, 4-CF , and 4-
3
NO , provided the corresponding products in 82% (3b), 78%
2
(
3c), 71% (3d), and 51% (3e) yields with 87%−91% ee. The
electron-donating 4-methoxy sulfoxide 2f furnished the
product (3f) in 94% yield with 83% ee, using 10 mol %
catalyst. Sterically hindered aryl 2-(trimethylsilyl)ethyl sulf-
oxides bearing 2-tolyl or 1-naphthyl provided products in
78%−80% yield, but with reduced enantioselectivities of 79%
(3g) and 63% (3h). Sulfoxides with heteroaryl moieties are
very important in medicinal chemistry but can be difficult to
Scheme 2. Substituted 2-(Trimethylsilyl)ethyl Sulfoxide as
the Sulfenate Anion Precursors for Pd-Catalyzed Cross-
Couplings with Aryl Bromides
16
prepare by traditional methods, because of overoxidation.
The 4-pyridyl-substituted sulfenate anion that formed 3i was a
good substrate, giving 68% yield and 91% ee.
Next, the scope of alkenyl electrophiles was explored with 1a
under the optimized conditions (Scheme 4). We first examined
styrenyl bromides but yields under the optimized conditions
were low. After screening a series of additives, we found that
the yields improved by adding 15-crown-5 or increasing the
reaction temperature. Enantioenriched sulfoxides derived from
styrenyl bromides bearing 4-F (3j) or electron-donating groups
(3k, 3l, 3m) gave 70%−91% yield and 70%−83% ee. (Z)-2-
We initially screened the reaction between 2-(trimethyl-
silyl)ethyl phenyl sulfoxide (1a, 1 equiv) and 2-bromopropene
(
2a, 2 equiv) with 5 mol % Pd(dba) , 24 chiral phosphine
2
ligands (10 mol % for monodentate ligands and 5 mol % for
bidentate ligands) and CsF (3 equiv) in 100 μL 2-Me-THF at
0 °C for 24 h (see the Supporting Information for details). Of
8
Table 1. Optimization of Asymmetric Vinylation of Sulfenate Anions
a
entry
Pd source
solvent
temperature, t [°C]
concentration [M]
assay yield, AY [%]
enantiomeric excess, ee [%]
1
2
3
4
5
6
7
8
Pd(dba)2
Pd(dba)2
2-Me-THF
THF
THF
THF
THF
THF
THF
THF
80
80
80
50
40
27
40
40
0.5
0.5
0.5
0.5
0.5
0.5
0.25
1.0
79
83
85
85
71
77
79
84
89
93
87
88
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
[Pd(allyl)Cl]2
b
87 (85 )
10
30
80
a
1
b
As determined by H NMR, using 0.1 mmol CH Br as internal standard. Isolated yield.
2
2
B
DOI: 10.1021/acs.orglett.8b03943
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
Scheme 3. Substrate Scope of Aryl 2-(trimethylsilyl)ethyl
Sulfoxides in Pd-Catalyzed Enantioselective Cross-
Couplings with 2a
Scheme 5. Substrate Scope of Aryl Electrophiles in Pd-
Catalyzed Enantioselective Cross-Coupling with 1a
were R, as determined by comparison of their optical rotations
17
with reported values.
The benzylic proton of an aryl benzyl sulfoxide can be
deprotonated and arylated with Pd catalysts and aryl bromides
under basic condition. Aryl sulfenate anions are ultimately
15d
generated. To explore the viability of our method to prepare
sensitive enantioenriched sulfoxides, the benzyl sulfenate anion
derived from 1j was subjected to the reaction conditions (2.5
a
One mmol reaction was conducted and gave 3a with 79% yield and
b
8
9% ee. [Pd(allyl)Cl] , 5 mol %; SL-J002-1, 10 mol %.
2
mol % [Pd(allyl)Cl] , 5 mol % SL-J002-1, 1j (0.5 mmol),
2
bromobenzene (1.0 mmol), CsF (1.5 mmol), 15-crown-5 (0.5
mmol), 0.5 mL THF at 80 °C for 24 h). The desired product
was formed in 92% AY with only 45% ee. We then screened 24
different chiral phosphine ligands to improve the enantiose-
lectivity of this substrate (see the Supporting Information for
details). We found that SL-M004-1 was the best ligand, in
terms of yield and enantioselectivity. When the scale increased
to 0.1 mmol of 1j, this ligand provided the desired product in
Scheme 4. Substrates Scope of Alkenyl Electrophiles in Pd-
Catalyzed Enantioselective Cross-Coupling with 1a
9
4
0% yield and 57% ee at 80 °C. Lowering the temperature to
0 °C gave higher enantioselectivity (73% ee); however, the
yield decreased to 13%. Increasing the amount of 15-crown-5
to 15 equiv further improved the ee to 80% with an isolated
yield of 92% at 40 °C (Scheme 6). Under these optimized
conditions, 2-propyl-2-(trimethylsilyl)ethylsulfoxide (1k) and
phenethyl-2-(trimethylsilyl)ethylsulfoxide (1l) were examined,
giving 3v (45% yield, 80% ee) and 3w (90% yield, 49% ee).
The absolute configurations of 3u and 3w are S, as determined
a
b
c
One equiv 15-crown-5. 60 °C. Two equiv of 1-cyclohexenyl
trifluoromethanesulfonate was employed.
Scheme 6. Pd-Catalyzed Enantioselective Cross-Coupling of
the Alkyl Sulfenate Anion with 2m
Bromo-2-butene provided the product 3n in 88% yield and
8
5% ee without addition of crown ether. For reasons that are
unclear, the cyclic electrophile 1-bromocyclohexene decom-
posed under the reaction conditions. Use of the corresponding
vinyl triflate furnished the product 3o in 44% yield and 92% ee.
Considering the mild nature of the optimized conditions, we
envisioned that this system could be extended to sensitive aryl
and heteroaryl bromides (Scheme 5). Aryl bromides bearing
nitrile (3p), aldehyde (3q), and ester (3r) groups all gave
moderate to high yields (75%, 62%, and 92%, respectively)
with good enantioselectivities (83%−87% ee). 5-Bromoindole
was also tolerated without protection of the nitrogen,
providing 3s in 65% yield with 85% ee. When 2-
(
trimethylsilyl)ethyl phenyl sulfoxide was coupled with 3-
bromothiophene, the yield of the desired product (3t) was
4% with 90% ee. The absolute configuration of 3p, 3q, and 3r
9
C
DOI: 10.1021/acs.orglett.8b03943
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
by comparison of the optical rotations with the literature
data.
Treatment of Viral Diseases Caused by Single Stranded RNA Virus,
Flaviviridae Virus or Hepatitis Virus, such as Viral Hepatitis.
International Patent No. WO2010009970 A1, 2010.
1
7
In summary, we have developed a versatile approach to
synthesize a variety of enantioenriched sulfoxides from both
aryl and alkyl sulfenate anions in moderate to high
enantioselectivities and in good yields. This is the first catalytic
asymmetric method for the generation of enantioenriched vinyl
sulfoxides. Key to the success of this method is the fluoride-
triggered elimination of the sulfenate anions at 40 °C, which
can be captured by palladium(II) catalysts bearing an
enantioenriched bidentate phosphine ligand.
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ASSOCIATED CONTENT
Supporting Information
■
*
S
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.or-
glett.8b03943.
Procedures, characterization data for all new compounds
(PDF)
67, 4378. (f) Trost, B. M.; Ryan, M. C.; Rao, M.; Markovic, T. Z.
Construction of enantio-enriched [3.1. 0] bicycles via a ruthenium-
catalyzed asymmetric redox bicycloisomerization reaction. J. Am.
Chem. Soc. 2014, 136, 17422. (g) Wang, M.; Wei, J. P.; Fan, Q. L.;
Jiang, X. F. A practical synthesis of novel chiral sulfoxide-nitrogen
ligands. Tetrahedron 2016, 72, 2671. (h) Pulis, A. P.; Procter, D. J. C−
H Coupling Reactions Directed by Sulfoxides: Teaching an Old
Functional Group New Tricks. Angew. Chem., Int. Ed. 2016, 55, 9842.
(5) Hayes, P.; Maignan, C. Ready access to the 6,8-dioxabicyclo
AUTHOR INFORMATION
Corresponding Author
E-mail: pwalsh@sas.upenn.edu.
■
*
ORCID
Chen Wu: 0000-0001-7427-1661
Xiaoxia Liang: 0000-0001-5002-5327
Patrick J. Walsh: 0000-0001-8392-4150
Notes
3
.2.1 octane ring system using asymmetric heterocycloaddition
induced by a chiral sulfoxide: application to the total synthesis of
the Mus musculus pheromone. Tetrahedron: Asymmetry 1999, 10,
1041.
The authors declare no competing financial interest.
(
6) (a) Posner, G. H.; Mallamo, J. P.; Miura, K. High asymmetric
ACKNOWLEDGMENTS
P.J.W. thanks the National Science Foundation (No. CHE-
464744) for financial support.
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DOI: 10.1021/acs.orglett.8b03943
Org. Lett. XXXX, XXX, XXX−XXX