Tandem Peterson olefination and chemoselective asymmetric hydrogenation of β-hydroxy silanes

Article abstract of DOI:10.1039/c8sc05261a

Here, we report the first Ir-N,P complex catalyzed tandem Peterson olefination and asymmetric hydrogenation of β-hydroxy silanes. This reaction resulted in the formation of chiral alkanes in high isolated yields (up to 99%) and excellent enantioselectivity (up to 99% ee) under mild conditions. Modification of the reaction conditions provides a choice to transform either an olefin or the β-hydroxy silane in a chemoselective manner. Additionally, based on this method, an expedient enantioselective synthesis of (S)-(+)-α-curcumene, from a simple ketone, was accomplished in two steps with 75% overall yield and 95% ee.

Full text of DOI:10.1039/c8sc05261a

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DOI: 10.1039/C8SC05261A
Journal Name
ARTICLE
Tandem Peterson Olefination and Chemoselective Asymmetric
Hydrogenation of β-Hydroxy Silanes†
Received 00th January 20xx,
Accepted 00th January 20xx
Suppachai Krajangsri, ‡ Haibo Wu, ‡a Jianguo Liu, ‡a Wangchuk Rabten, Thishana Singh and
a
a
b
a
Pher G. Andersson*
DOI: 10.1039/x0xx00000x
Here, we report the first Ir-N,P complex catalyzed tandem Peterson olefination and asymmetric hydrogenation of β-
hydroxy silanes. This reaction resulted in the formation of chiral alkanes in high isolated yields (up to 99%) and excellent
enantioselectivity (up to 99% ee) under mild conditions. Modification of the reaction conditions provides a choice to
transform either an olefin or the β-hydroxy silane in a chemoselective manner. Additionally, based on this method, an
expedient enantioselective synthesis of (S)-(+)-α-curcumene, from a simple ketone, was accomplished in two steps with
www.rsc.org/
7
5% overall yield and 95% ee.
center, however, it is quite challenging to achieve excellent
1
1
Introduction
The chiral benzylic hydrocarbon motif is widespread in various
enantioselectivity
since it is much more difficult to
distinguish the two prochiral faces of the terminal olefin.
Utilizing directing groups, Zhou’s group
group successfully attained asymmetric hydrogenation of
1
2a,b
and Zhang’s
1
functional molecules and bioactive natural products.
1
2c
Examples of such molecules include the anaesthetic propofol
analog HSK3486,2 the bisabolanes sesquiterpenes (S)-(+)-
curcumene and (S)-(+)-ar-turmerone with antibacterial
3
4
activity, (+)-helianane with antifungal and cytotoxic activities
5
and ileabethoxazole with strongly antimycobacterial activity
(
a) Functional molecules and natural products with chiral benzylic hydrocarbon motif
(Fig. 1a). Notably, the induction of the benzylic chiral center is
O
the crucial but challenging step in synthesis of these
compounds and has attracted considerable attention.
N
OH
6
X
Me
O
H
Asymmetric hydrogenation, has over the past decades, been
successfully developed to achieve excellent enantioselectivity
Me
OH
Me Me
ileabethoxazole
Me
Me
HSK3486
anesthetic)
X= (H, H) (S)-(+)-curcumene
(
X= O
(S)-(+)-ar-turmerone
(+)-helianane
7
for a wide range of substrates. The reduction of olefins
(
b) Carboxy-directed asymmetric hydrogenation of 1,1-disubstituted olefin (Zhou, 2012;
8
usually involves iridium, ruthenium, or rhodium complexes.
Zhang, 2018)
Iridium catalysts have the outstanding advantage of not
requiring a chelating functional group adjacent to the C=C
bond to achieve high reaction activity and selectivity. In
addition to well-known Ir, Rh and Ru catalyst systems, cobalt,
iron and nickel catalysts recently have recently proved to be an
CO2H
CO2H
Ir or Ru Catalyst
H2
decarboxylation
R
R
R
chiral benzylic hydrocarbon
(
c) Iridium catalyzed asymmetric hydrogenation of 1,1-disubstituted olefin (Diéguez, 2013)
t-Bu
9
effective alternative method for asymmetric hydrogenation.
[Ir(cod)(L*)]BArF
R
R
O
O
Furthermore, chemoselectivity and regioselectivity are still
challenging to attain and there are only a few reported
N
O
P
(R)ax
H2
chiral benzylic
hydrocarbon
L*
t-Bu
1
0
examples highlighting this feature.
(
d) Tandem Peterson olefination and chemoselective asymmetric hydrogenation (this work)
Asymmetric hydrogenation of 1,1-disubstituted olefins was
expected to be a direct route to access the benzylic chiral
1
bar H2,
OH
R2
0.5 mol% Ir-catalyst
CH2Cl2, r.t. 1 h
Peterson
SiMe3
R2
R2
R1
R1
R1
asymmetric
elimination
hydrogenation
chiral benzylic
hydrocarbon
a. Department of Organic Chemistry, Stockholm University, Arrhenius Laboratory,
low catalyst loading
new catalysts
mild conditions
high yield & high enantioselectivity
1
06 91, Stockholm, Sweden. Email: pher.andersson@su.se
controllable chemoselectivity
OH
b.
School of Chemistry and Physics, University of Kwazulu-Natal, Private Bag
X54001, Durban, 4000, South Africa.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
OH
R1
H2
R1
H2
SiMe3
R1
SiMe3
+ Ar
R1
Ar
+ Ar
Ar
no base Ar
R1+
Ar
†
R1
base
R2
di,trisubstituted
R2
R2
‡
Suppachai Krajangsri, Haibo Wu and Jianguo Liu contributed equally.
Fig.1 Asymmetric hydrogenation to construct chiral benzylic
hydrocarbon motif.
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Table.1 Optimization of asymmetric hydrogenationa
(a) Unexpected Peterson elimination/asymmetric hydrogenation cascade (our previous study)
OH
OH
o-Tol o-Tol
P
+ -BArF
0
.5 mol% catalyst HC-2
1
mol % Ir-catalyst
bar H2
Toluene, r.t. 16 h
SiMe3
Ir(COD)
N H
TMS
+
3
N
Ph
H , r.t. 1 h
2
99% yield, 53% ee
1a
Solvent
2
2a
2a (Yieldb/%)
3a
S
(
b) Vinylogous Peterson elimination of allylic alcohol (Mazet, 2017)
Pressure (bar)
1
b
3a (eec /%)
Entry
1
3a (Yield /%)
t-Bu t-Bu
+ -BArF
Me3Si
P
CH Cl2
-
>99
95
Ir
N
5
mol% HBArF
5
mol%
OH
2
3
Benzene
PhCF3
Toluene
THF
1
1
24
25
76
75
9
1
H2 activation,
THF, 23°C, 24 h
THF, 23°C, 24 h
93
94
Fig.2 Peterson elimination and asymmetric hydrogenation.
4
5
1
1
62
38
1
,1-disubstituted olefins with high enantioselectivity (Fig. 1b).
The use of novel iridium phosphite-pyridine catalysts, by the
Diéguez’s group1 resulted in highly selective asymmetric
hydrogenation of a wide range of terminal olefins (Fig. 1c). We
recently achieved significant improvement in the development
of Ir-N,P-complexes for the asymmetric hydrogenation of di-,
tri- and tetrasubstituted olefins. Among these, substrates with
the silane group have raised much interest.
study that we conducted on the asymmetric hydrogenation of
secondary allylic alcohols, a substrate containing the β-hydroxy
silane moiety was evaluated (Fig. 2a). Instead of attaining the
mono-hydrogenated product of trisubstituted olefin, the fully
hydrogenated alkane was observed as the only product. In
a tandem reaction of Peterson elimination and
asymmetric hydrogenation occurred due to the acidic
medium15 created by activation of the iridium catalyst.
Recently, Mazet and co-workers reported
Peterson elimination of allylic alcohols catalyzed by an Ir-N,P
complex, where hydrogen gas was involved in the activation of
the catalyst to generate the iridium hydride species (Fig. 2b).
The β-hydroxy silane compounds are well-known as important
>99
-
-
2d
6
7
8
CH2Cl2
2
10
20
50
>99
>99
>99
90
83
73
-
CH Cl2
-
-
2
CH Cl2
1
0e,13
In a previous
a
Reaction conditions: 0.05 mmol substrate, 0.5 mol% catalyst, 0.5
b
1
mL CH
product.
2
Cl
2
.
Determined by H NMR spectroscopy of the crude
c
Determined
by
chiral
GC
analyses.
1
4
the ideal conditions for this reaction was 1 bar hydrogen with
CH Cl as the solvent.
2
2
fact,
Initially, the new iridium phosphite-oxazoline complex HC-2
was found to be an efficent catalyst for the model reaction in
the beginning. To further evaluate the potential for steric and
electronic tuning, the substituent on the oxazoline ring was
changed from furan (HC-1,2,3,4,5) to thiophen (HC-6,7,8) and
the heterocycle was attached to the ligand at different
positions and substituents were also varied (Table 2). Variation
a vinylogous
1
6
1
7
intermediates for olefination,
however their use as
substrates for asymmetric hydrogenation have never been
reported. Herein, we describe the first iridium catalyzed
tandem Peterson elimination/olefination and asymmetric
hydrogenation of β-hydroxy silanes to provide efficient access
to the chiral benzylic hydrocarbon motif. Under different
conditions, controllable chemoselectivity between β-hydroxy
silanes and other olefins could be obtained (Fig. 1d).
Table.2 Evaluation of new Ir-N,P catalystsa
OH
0.5 mol% catalyst
TMS
1 bar H2, CH2Cl2, r.t. 1 h
O
O
1b
3b
BArF-
Ar(Het)
=
O
O
O
O
O
O
P
O
Ir
HC-1
HC-2
HC-3
HC-4
Ph
Ph
N
O
O
O
O
O
=
Results and discussion
Our initial investigation began with the cascade Peterson
Ar(Het)
HC
O
S
S
S
(S)
HC-5
HC-6
HC-7
HC-8
elimination and asymmetric hydrogenation of β-hydroxy silane
b
c
b
c
Entry
Ir Cat.
Conv. (%)
ee (%)
Entry
Ir Cat.
Conv. (%)
ee (%)
1
to optimize the reaction conditions (Table 1). It was found
that CH Cl was the best solvent for this reaction, giving high
2
2
1
2
3
4
HC-1
HC-2
HC-3
HC-4
> 99
> 99
> 99
> 99
95
97
98
95
5
6
7
8
HC-5
HC-6
HC-7
HC-8
> 99
> 99
> 99
> 99
96
96
97
96
conversion within a short reaction time and excellent ee. Other
solvents retarded the hydrogenation and resulted in an
incomplete reaction that contained olefin 2a in the product
mixture (entries 2-5). Regarding the effect of hydrogen
pressure, it was found that increased H
enantioselectivity (entries 6-8). Hence, it was established that
2
pressure lowered the
a
Reaction conditions: 0.05 mmol substrate, 0.5 mol% catalyst, 0.5
b
1
mL CH
2
Cl
2
.
Determined by H NMR spectroscopy of the crude
c
product. Determined by chiral GC analyses.
2
| J. Name., 2012, 00, 1-3
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DOI: 10.1039/C8SC05261A
Table.3 Substrate scopea
(a) Competition experiment betweenβ-hydroxy silane and disubstituted olefins
OH
OH
1 bar H2
1 bar H2
0.5 mol% HC-2
CH2Cl2, r.t. 1 h
CO2Me
2
CO Me
R’
0
.5 mol% catalyst HC-3
R’
+
+
R
R
TMS
TMS
CH2Cl2, r.t. 2 h
1a
4
3a
9% yield
4% ee
4
1
3
9
9
9
9% recovery
OH
1
bar H2
Ph
Ph
0
.5 mol% HC-2
CH2Cl2, r.t. 1 h
+
+
TMS
F
F
3
a
3c
95% yield
95% ee
3d
76% yield
95% ee
3e
3f
1a
5
3a
9% yield
4% ee
5
9
9
9
9
9% yield
5% ee
98% yield
99% ee
98% yield
94% ee
99% recovery
(
b) Competition experiment between β-hydroxy silane and trisubstituted olefins
OH
1 bar H2
Ph
0.5 mol% HC-5
CH2Cl2, r.t. 1.5 h
t-Bu
+
Ph
F
Br
MeO
F3C
t-Bu
3
g
3h
96% yield
95% ee
3b
3i
+
TMS
8
9
3% yield
4% ee
98% yield
97% ee
89% yieldb
3e
6
9
4% ee
1e
6
99% yield
9% ee
9
9% recovery
9
Cl
Br
Ph
OH
1
bar H2
CO2Et
1.0 mol% HC-5
CH2Cl2, r.t. 1.5 h
CO2Et
t-Bu
t-Bu
+
MeO2C
3
j
3k
3l
96% yieldb
6% ee
3m
99% yieldb
+
TMS
9
9
2% yield
4% ee
98% yield
93% ee
3e
7
1e
7
9
90% ee
99% yield
99% recovery
99% ee
(
c) Reverse chemoselectivity under basic condition
a
Reaction conditions: 0.40 mmol substrate, 0.5 mol% catalyst, 4
OH
OH
7
5 bar H2
mL CH
2
Cl
2
. Yield refers to isolated yield. ee was determined by
Ph
Ph
t-Bu
0.5 mol% catalyst IC
t-Bu
b
+
+
TMS
chiral SFC or GC analyses. Reaction conditions: 2 bar H
mol% catalyst.
2
, 3 h, 1
PhCF , K PO , r.t. 3 h
TMS
3
3
4
8
1e
1e
6
tBu
99% yield
99% ee
tBu
9
9% recovery
P
N
Ir(COD)
N
of the heteroaromatic ring did not significantly affect the
reactivity of β-hydroxy silane substrate, with all catalysts giving
full conversion to the hydrogenated product in excellent yield.
Formation of the isomerized, trisubstituted olefin was not
observed in any of the reactions. An improvement in
enantioselectivity was observed for catalyst HC-7 (97% ee) and
catalyst HC-3 (98% ee).
OMe
catalyst IC
MeO
OH
OH
5
0 bar H2
2
CO Et
CO2Et
t-Bu
t-Bu
1.0 mol% catalyst IC
+
+
TMS
TMS
PhCF3, K3PO4, r.t. 2 h
9
1e
9% recovery
1e
7
99% yield
6% ee
9
9
Scheme.1 Chemoselective asymmetric hydrogenation.
With the optimized reaction conditions established, we
prepared and tested several different substrates to evaluate
the scope of the reaction (Table 3). Substrates having aliphatic
substituents such as ethyl, n-butyl, i-propyl, cyclohexyl, and t-
butyl (3a-3f) provided the desired product in excellent yield
and high enantioselectivity of up to 99% ee. The effect of
varying the substituents on the phenyl ring was also
investigated. Electron-withdrawing groups as well as electron-
donating groups at the para-position (3g-3i) did not affect the
efficiency of the reaction. Excellent isolated yields of up to 99%
and ees up to 95% were achieved. Electron-withdrawing
groups at the meta-position (3j,3k) also gave very good results.
Substrate 1l, containing the benzyl group, gave the desired
product in excellent yield of 96% and high ee of 97%. No trace
of the isomerized trisubstituted olefin was observed in the
reaction. Substrate 1m, bearing the ester functional group was
converted to the desired product in excellent yield of 99% with
good ee of 90%.
Given the very mild reaction conditions and the high reaction
rates for the Peterson elimination-hydrogenation, we were
compelled to investigate the degree of chemoselectivity in the
asymmetric hydrogenation of β-hydroxy silanes compared to
some common olefins (Scheme 1). In this study, β-hydroxy
silanes and different olefins were mixed and subjected to the
standard reaction conditions. We observed that 1a yielded the
completely hydrogenated product in a short reaction time with
excellent ee while the olefins remained unaffected. The trans
disubstituted olefins 4 and 5 were not hydrogenated whereas
1
a was fully converted to the desired product (Scheme 1a).
Trisubstituted olefins 6 and 7 were also tested in the
hydrogenation, no hydrogenation of the olefins was detected,
while full conversion of β-hydroxy silane 1e was observed
(Scheme 1b).
We also investigated the possibility of selective hydrogenation
of an olefin in the presence of a β-hydroxy silane. Our rational
was that, since the Peterson olefination requires acidic
condition, and then a less acidic iridium catalyst would
hydrogenate the olefin without catalyzing the Peterson
reaction. When a mixture of trans-α-methylstilbene 6 or trans-
β-methylcinnamate 7 and β-hydroxy silane 1e was subjected
to a higher hydrogen pressure using catalyst IC in the presence
of K PO , as expected, these reactions gave a complete change
3 4
in chemoselectivity and resulted in a selective hydrogenation
of the olefin, leaving the β-hydroxy silane intact (Scheme 1c).
The basic additive (K PO ) has proved to be efficient in
3 4
preventing the decomposition of the acid-sensitive starting
material or hydrogenated product under the acidic
environment, which was generated in the iridium catalyzed
asymmetric hydrogenation. These results demonstrate that a
highly chemoselective transformation of either an olefin or a
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The synthetic utility of this method was highlighted by the
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DOI: 10.1039/C8SC05261A
OH
facile synthesis of bisabolane sesquiterpene (S)-(+)-curcumene
(
O
O
O
TMSCH2MgCl
Et2O, r.t. 24 h
EtO
EtO
Scheme 3b). Despite its simple structure, the benzylmethyl
TMS
O
chiral center poses a significant challenge in the asymmetric
synthesis, and it has evolved as a popular test target for
77%
10
11
2
bar H2
.0 mol% HC-3
CH2Cl2, r.t. 3 h
O
1
8
demonstrating the proficiency of new asymmetric processes.
1
EtO
+
EtO
11
The synthesis began with treatment of simple ketone 14 with
Peterson reagent smoothly affording the β-hydroxy silane
compound 15 in quantitative yield. Subsequent asymmetric
hydrogenation of 15 directly furnished the target natural
product (S)-(+)-curcumene with 76% yield and 95% ee. This
12
9
3% yield (95:5)
13
9
5% ee
Scheme.2 Intramolecular chemoseletive functionalization.
β-hydroxy silane is possible by selecting the appropriate two-step, highly enantioselective synthesis represents one of
reaction conditions.
the most efficent ways to access (S)-(+)-curcumene.
Based on the completely opposite chemoselectivity that was
obtained upon addition of base, we assumed that the in situ
generated irdium dihydride catalyst acted as a Brønsted acid in
Conclusions
1
5d
the eliminaltion step.
Alternatively, the iridium dihydride In summary, we have demonstrated an iridium catalyzed
intermidiate might be directly involved in promoting the tandem Peterson olefination and asymmetric hydrogenation of
1
6
Peterson elimination. However, since Peterson elimination of β-hydroxy silanes under particularly mild conditions and low
β-hydroxy silane 1e did not occur during the hydrogenation of catalyst loading using novel Ir-N,P catalysts. The method we
olefins 6 and 7 under basic conditions (Scheme 1c), it is have developed provided efficient access to the chiral benzylic
suggested that the iridium dihydride is not directly responsible hydrocarbon motif. It was found that the reaction is highly
for the elimination. In a control experiment it was found that chemoselective and that it could be tuned to selectively
the addition of a bulky, non-coordinating base such as DTBMP transform either an olefin or a β-hydroxy silane. By use of this
completely inhibited the elimination (see the Electronic methodology, we achieved the asymmetric syntheses of
Supplementary Information for details).
natural product (S)-(+)-curcumene in two steps with high yield.
The potential of the reaction was investigated by testing a Further application of this strategy for the synthesis of more
substrate that contained both an olefin as well as an ester structurally related natural products is ongoing in our
group (Scheme 2). The unsaturated keto ester 10 reacted laboratory.
selectively with TMSCH MgCl to give 11 in 77% isolated yield.
2
Using catalyst HC-3, under standard reaction conditions,
substrate 21 underwent Peterson olefination/hydrogenation Conflicts of interest
to give the desired product in a highly chemoselective manner
with good ee (95%).
There are no conflicts to declare.
To further demonstrate the practical application of this
methodology, a gram scale reaction was carried out. The
reaction was conducted in CH Cl with 1 bar H at room
2 2 2
Acknowledgements
The Swedish Research Council (VR), Stiftelsen Olle Engkvist
Byggmästare and The Swedish Energy Agency supported this
work. J. L. thanks the Guangzhou Elite Scholarship Council for
the PhD fellowship.
temperature in the presence of 1.0 mol% catalyst HC-3,
affording the desired product 3f in high yield and excellent ee
(Scheme 3a). When compared to the small scale reaction, it
was noted that the yield was not affected and the
enantioselectivity slightly increased.
Notes and references
1
For selected examples, see: (a) A. E. Wright, S. A. Pomponi,
O. J. McConnell, S. Kohmoto and P. J. McCarthy, J. Nat. Prod.,
(a) Gram scale reaction
1
987, 50, 976. (b) H. Matsuda, T. Morikawa, K. Ninomiya and
OH
1
bar H2
.0 mol% HC-3
CH2Cl2, r.t. 1 h
M. Yoshikawa, Bioorg. Med. Chem., 2001, 9, 909. (c) A. D.
Rodríguez and C. Ramírez, J. Nat. Prod., 2001, 64, 100.(d) F.
A. Macías, R. M. Varela, A. Torres, J. M. G. Molinillo and F. R.
Fronczek, Tetrahedron Lett., 1993, 34, 1999. (e) V. Roussis, Z.
Wu, W. Fenical, S. A. Strobel, G. D. Van Duyne and J. Clardy,
J. Org. Chem., 1990, 55, 4916. (f) C. A. Harvis, M. T. Burch
and W. Fenical, Tetrahedron Lett., 1988, 29, 4361. (g) S. A.
Look, W. Fenical, R. S. Jacobs and J. Clardy, Proc. Natl. Acad.
Sci., 1986, 83, 6238. (h) S.-e. Muto, M. Bando and K. Mori,
Eur. J. Org. Chem., 2004, 2004, 1946. (i) S. P. Chavan and H.
S. Khatod, Tetrahedron: Asymmetry, 2012, 23, 1410.
1
TMS
1
f
3f
1
.0 g, 3.6 mmol
98% yield, 96% ee
(
b) Synthesis of (S)-(+)-curcumene
1
bar H2
O
OH
TMSCH2MgCl
Et2O, r.t. 48 h
1mol% HC-3
PhCF , r.t. 1h
3
TMS
1
4
99% yield
(
S)-(+)-curcumene
15
76% yield, 95% ee
2
(a) L. Qin, L. Ren, S. Wan, G. Liu, X. Luo, Z. Liu, F. Li, Y. Yu, J.
Liu and Y. Wei, J. Med. Chem., 2017, 60, 3606. (b) Y. Wei, G.
Scheme.3 Scale-up preparation and synthesis application.
4
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Qiu, B. Lei, L. Qin, H. Chu, Y. Lu, G. Zhu, Q. Gao, Q. Huang, G.
Qian, P. Liao, X. Luo, X. Zhang, C. Zhang, Y. Li, S. Zheng, Y. Yu,
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Chemical Science
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DOI: 10.1039/C8SC05261A
Tandem Peterson olefination and asymmetric hydrogenation of β-hydroxy
silanes provides an efficient route to access the chiral benzylic hydrocarbon. The
chemoselectivity can be tuned by the addition of base.
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