Copper-Catalyzed Enantioselective Domino Arylation/Semipinacol Rearrangement of Allylic Alcohols with Diaryliodonium Salts

Article abstract of DOI:10.1002/chem.201703563

A copper-catalyzed enantioselective arylative semipinacol rearrangement of allylic alcohols was developed. In the presence of a catalytic amount of an in situ generated chiral copper-bisoxazoline complex, reaction of allylic alcohols with diaryliodonium salts afforded spirocycloalkanones in high yields with high diastereo- and enantioselectivities. A two-point binding model engaging the carbon–carbon double bond and the proximal hydroxyl group was proposed to be responsible for the highly efficient chirality transfer.

Full text of DOI:10.1002/chem.201703563

A Journal of
Accepted Article
Title: Copper-Catalyzed Enantioselective Domino Arylation/
Semipinacol Rearrangement of Allylic Alcohols with
Diaryliodonium Salts
Authors: Hua Wu, Qian Wang, and Jieping Zhu
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To be cited as: Chem. Eur. J. 10.1002/chem.201703563
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Copper-Catalyzed Enantioselective Domino Arylation/Semipinacol
Rearrangement of Allylic Alcohols with Diaryliodonium Salts
Hua Wu, Qian Wang, Jieping Zhu*
Abstract:
A
copper-catalyzed
enantioselective
arylative
group on the same subject prompted us to communicate herein
our own results.[11] Spirocycloalkanones obtained in this
process[12] are privileged scaffold in the development of chiral
ligands/organocatalysis[13] and are known precursors for the
synthesis of acetylcholinesterase and monoamine oxidase.[14]
semipinacol rearrangement of allylic alcohols was developed. In
the presence of a catalytic amount of an in situ generated chiral
copper-bisoxazoline complex, reaction of allylic alcohols with
diaryliodonium salts afforded spirocycloalkanones in high yields
with high diastereo- and enantioselectivities. A two-point binding
model engaging the carbon-carbon double bond and the proximal
hydroxyl group was proposed to be responsible for the highly
efficient chirality transfer.
a) Gaunt's work
O
HO
HO
R
Cu(I)
R
R
+
Ph2IOTf
Ph+
R = Me, H
Ph
b) Toste and Kim's work
O
R
HO
R
Semipinacol rearrangement of allylic alcohols triggered by
electrophilic activation is an important transformation in organic
synthesis.[1] The development of enantioselective version has
been achieved only recently thanks to the advance of the
organocatalysis.[2,3] Most of these asymmetric processes were
initiated by protonation, halogenation and epoxidation leading
to the concurrent formation of C-H or C-X bonds (X = halogen,
O). Examples of arylative or alkylative semipinacol
rearrangements were scarce.[4,5] In their 2012 paper dealing
with the copper-catalyzed alkene arylation with diaryliodonium
salts, Gaunt provided two examples of Cu-catalyzed synthesis
of 2-benzylated cyclopentanones from vinylcyclobutan-1-ols
and proposed that the reaction might be initiated by Friedel-
Crafts type reaction of an alkene with a phenyl cation
equivalent (Scheme 1a).[6] Two years later, Toste reported a
detailed study on the arylative semipinacol rearrangement
using aryldiazonium salt as arylating regent under dual
Au(I)/Ru(bpy)3(PF6)2, visible light
or Ru(bpy)3(PF6)2, visible light
n
ArN2BF4
+
n
n = 0, 1
Ar
c) This work: Enantioselective arylative semipinacol rearrangement
O
HO
R'
R
Ar
*
L
L
R
AsF6
Mes
CuX
L
R
Cu
n
n
+
Ar
I
O
R'
n = 1, 2
R'
Ar
*
L
n
1
2
3
OH-directed enantioselective arylation
Scheme 1. Domino arylation/semipinacol rearrangement of allylic alcohols.
Table 1. Optimization of the reaction conditions.[a]
OH
+
Cu(OTf)2 (0.1 equiv )
Ligand (0.15 equiv)
O
X
I
gold/photoredox
catalytic
conditions
(Scheme
1b).[7]
Ph
Mes
Ph
DTBP (2.0 equiv)
DCM
Subsequently, Kim reported that the same transformation can
be realized in the absence of gold catalysis.[8]
1a
Entry Ligand
2a
3a
X
T (oC) Y (%)[b] d.r.[c] ee (%)[d]
Being aware of the challenges associated with the
1
2
3
4
5
7
8
9
L1
L2
L3
L4
L5
L6
L7
L8
L8
L8
L8
L8
L8
OTf
OTf
OTf
OTf
OTf
OTf
OTf
OTf
BF4
50
50
50
50
50
50
50
50
50
50
50
50
RT
trace
67
trace
trace
65
70
54
75
80
85
87
82
88
trace
89
-
-
development
of
asymmetric
arylative
semipinacol
5.8:1
-
-
9(53)
-
-
rearrangement and in connection with our ongoing research
program dealing with enantioselective dicarbofunctionalization
of alkenes.[9] We set out to examine the copper-catalyzed
enantioselective arylative semipinacol rearrangement of allylic
alcohols 1 using diaryliodonium salts 2 as electrophilic arylating
reagents (Scheme 1c). On the basis of literature precedents,[10]
we reasoned that the hydroxyl group could potentially serve as
an anchoring point to engage the allylic alcohol 1 in a two-point
binding model with the Ar-Cu(III) species. In the presence of an
appropriate chiral ligand, one should be able to differentiate the
two faces of the double bond, achieving therefore the
enantioselective aryl transfer. A recent paper from Gaunt’s
2.1:1
4.3:1
5.5:1
2.1:1
2.8:1
3.1:1
3.0:1
2.7:1
3.0:1
52(70)
5(38)
25(57)
75(74)
76(78)
86(85)
86(87)
86(84)
92(88)
10
11
12
13
14[e]
PF6
AsF6
SbF6
AsF6
AsF6
AsF6
15[e,f]
L8
L8
RT
RT
-
-
16[e,g]
3.3:1
93(93)
[a] 1a (0.1 mmol), 2a (0.13 mmol), Cu(OTf)2 (0.01 mmol), Ligand (0.015
mmol), DTBP (0.2 mmol), DCM (1.0 mL), T (oC), 12 h. [b] Total isolated
yields. [c] Determined by 1H NMR spectroscopy. [d] Determined by SFC
analysis on a chiral stationary phase. Values in the parenthesis is the ee of
the minor isomer. [e] The reaction was conducted at 0.3 mmol scale of 1a for
24 h. [f] Cu(MeCN)4PF6 (0.1 equiv) was used. [g] CuCl (0.1 equiv) was used.
DTBP = 2,6-di-tert-butylpyridine.
[*]
Dr. H. Wu, Dr. Q. Wang, Prof. Dr. J. Zhu
Laboratory of Synthesis and Natural Products
Institute of Chemical Sciences and Engineering
Ecole Polytechnique Fédérale de Lausanne
EPFL-SB-ISIC-LSPN, BCH 5304, 1015 Lausanne (Switzerland)
E-mail: jieping.zhu@epfl.ch
Arylative semipinacol rearrangement of 1-(1H-inden-3-
yl)cyclobutan-1-ol
(1a)
with
mesityl(phenyl)iodonium
trifluoromethanesulfonate (2a) was chosen as a benchmark
reaction. Heating a CH2Cl2 solution of 1a and 2a in the
presence of copper(II) triflate, PyBox L1 (Figure 1) and 2,6-di-
tert-butylpyridine (DTBP) afforded only a trace amount of the
Homepage: http://lspn.epfl.ch
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/chem.201703563
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rearranged product 3a (Table 1, entry 1). Using bidentate
(S,S)-diphenylbisoxazoline L2 as ligand under otherwise
identical conditions provided the desired product 3a in 67%
yield, albeit with only 9% ee (entry 2). With L5, ligand of choice
in Gaunt’s work,[11] 3a was isolated in 65% yield with 52% ee
under these non-optimized conditions. Further experiments
revealed that bisoxazoline L8 derived from (1R,2S)-2-amino-
1,2-diphenylethan-1-ol was the most effective (entry 9) leading
to 3a in 75% yield with ee of 75% and 74%, respectively, for
the two diastereoisomers. The influence of different
counteranions of the diaryliodonium salts on the reaction
outcome was next examined (entries 9-13) and AsF6 salt was
found to be optimal (entry 12). Subsequent survey of reaction
conditions varying the temperature and the copper sources
allowed us to further improve the reaction efficiency (entries
14-16). Overall, the optimum conditions found consisted of
performing the arylative semipinacol rearrangement of 1a in
CH2Cl2 (c 0.1 M) at room temperature in the presence of CuCl
(0.1 equiv), chiral bisoxazoline L8 (0.15 equiv) and DTBP (2.0
equiv). Under these conditions, spirocycloalkanone 3a was
obtained in 89% overall yield as a mixture of two separable
diastereomers (d.r. 3.3:1) with 93% ee for both isomers (entry
16). That the reaction proceeded at room temperature might
indicate the important role played by the proximal hydroxyl
O
OH
+
CuCl (0.1 equiv)
L8 (0.15 equiv )
AsF6
Mes
1
Ar
I
Ar
2
DTBP (2.0 equiv)
DCM, RT
1a
3b
2
3a
O
O
O
Me
F
Cl
3c
3d
85%, 4.3:1 d.r.
95% ee (95% ee)
95%, 3.0:1 d.r.
85%, 4.5:1 d.r.
95% ee (95% ee)
92% ee (92% ee )
O
O
O
Br
OMe
CF3
3g
3e
3f
66%, 2.1:1 d.r.
90% ee (90% ee)[a]
94%, 5.0:1 d.r.
91% ee (89% ee)[b]
89%, 4.5:1 d.r.
95% ee (94% ee)
Cl
O
O
F
O
MeO
3j
3h
3i
63%, 4.2:1 d.r.
90%, 4.0:1 d.r.
94% ee (94% ee)
47%, 6.1:1 d.r.
95% ee[c]
93% ee (93% ee)
Me
Me
O
O
O
S
3k
o
3m
3l
group since higher temperature (70 C) was generally required
71%, 3.1:1 d.r.
89% ee ( 90% ee)[c]
for the arylation of simple 1H-indene.[6]
73%, 2.9:1 d.r.
72%, 2.9:1 d.r.
87% ee (92% ee)
82% ee (84% ee)[a]
H
H
Scheme 2. Scope of the diaryliodonium salts with vinylcyclobutanol 1a. [a]
Cu(OTf)2 (0.1 equiv) as the catalyst at 50 °C. [b] Bis(4-
(trifluoromethyl)phenyl)iodonium hexafluoroarsenate was used. [c] Cu(OTf)2
(0.1 equiv) as the catalyst at 60 °C.
O
O
O
O
O
O
L3: R = Bn
L4: R = tBu
L5: R = Ph
N
N
N
N
N
N
N
Ph
Ph
R
R
tBu
tBu
L1
L2
R
O
R
O
O
O
O
O
Ph
Ph
N
N
N
N
N
N
CuCl (0.1 equiv)
L8 (0.15 equiv )
OH
Ph
Ph
O
Ph
Ph
Ph
Ph
AsF6
Mes
L6
L8
L7: R = 4-tBuC6H4
+
Ar
I
Ar
DTBP (2.0 equiv)
DCM, 50 °C
Figure 1. Structures of representative chiral ligands.
1b
2
3
O
O
O
Cl
With the optimized conditions in hand, the scope of this
enantioselective arylation/rearrangement cascade was next
explored. Diaryliodonium salts bearing electron-neutral,
F
3p
3n
3o
61%, >20:1 d.r., 94% ee 62%, >20:1 d.r., 94% ee 56%, >20:1 d.r., 93% ee
eletron-withdrawing
underwent the desired arylative semipinacol rearrangement to
and
electron-donating
substituents
Me
Me
O
O
O
generate spiro[4,4]nonan-1-ones 3 in good to high yields, with
CF3
moderate
diastereoselectivities
and
excellent
3q
3r
3s
Me
enantioselectivities (Scheme 2). Substituents at para, meta and
ortho positions were well tolerated (3b-3j). Strong electron-rich
aromatics underwent this transformation equally well by
performing the reaction at 50 or 60 °C in the presence of
copper triflate as catalyst (3f,3j). 3,5-Dimethylphenyl, 2-
naphthyl and heterocycle (2-thiophene) were transferred
without event (3k-3m). Both diastereomers of 3 were obtained
in excellent enantiomeric excesses and were fully
characterized. The absolute configuration of the minor isomer
3a was determined by single crystal X-ray diffraction analysis
to be (1S,2S).[15] Consequently, the (1R,2S) configuration was
assigned for the major stereoisomer. The sense of
stereoselectivity is in accord with Guant’s observation.
54%, >20:1 d.r., 91% ee[a] 66%, >20:1 d.r., 92% ee 43%, >20:1 d.r., 85% ee[b]
Scheme 3. Scope of the diaryliodonium salts with vinylcyclopentanol 1b. [a]
Bis(4-(trifluoromethyl)phenyl)iodonium hexafluoroarsenate was used. [b]
Cu(OTf)2 (0.1 equiv) as the catalyst at 50 °C.
Encouraged by the aforementioned results, we decided
to extend the reaction to vinylcyclopentanol 1b, a more
challenging substrate (ring strains: cyclobutane 26.7 kcal/mol,
cylopentane 7.4 kcal/mol). Gratefully,
a
series of
diaryliodonium salts with different electronic properties reacted
with 1b smoothly to provide the corresponding spiro[4,5]decan-
1-ones 3n-3s in good yields with excellent diastereo- and
enantioselectivities (Scheme 3). The high diastereoselectivity
observed in this series compared to that of vinylcyclobutanol
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10.1002/chem.201703563
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induced by the catalyst during the 1,2-alkyl migration step. This
result implied that the semipinacol rearrangement involving the
discrete cabocation intermediate as proposed previously might
not be the only pathway and that the copper catalyst could well
be involved in the rearrangement process.
1a is noteworthy. The diminished ring strain release going from
5- to 6-membered ring might render the 1,2-migration process
more selective.
A series of structurally diverse allylic alcohols was
evaluated to further probe the reaction scope (Scheme 4).
Vinylcyclobutanols with various substituents at different
positions on the benzene ring underwent the arylative
semipinacol rearrangement to furnish the desired products in
high yields with good diastereoselectivities and excellent
enantiomeric excesses (3t-3w). However, the dimethoxy-
Based on the results of these control experiments, a
possible reaction pathway is depicted in Scheme 6. Oxidative
addition of diaryliodonium salts 2 to the chiral Cu(I) complex A
would generate Ar-Cu(III) species B which, upon coordination
to both the hydroxyl group and the double bond would
generate chelate C. Enantioselective syn-carbocupration[16]
would afford intermediate D which, upon 1,2-alkyl migration
with concurrent cleavage of the C-Cu bond in an SN2 fashion,
would afford the major diastereomer of spirocycloalkanone 3
(voie a, Scheme 6). Formation of carbenium intermediate E
from C, as previously proposed for the arylation of electron-rich
alkenes, followed by semipinacol rearrangement could also be
operating (voie b).[6] Alternatively, the domino process could
also be initiated by semipinacol rearrangement from
intermediate C to F.[7,17] that would be converted to 3 by
reductive elimination with concurrent generation of the active
Cu(I) catalyst.[18] Further experiments and theoretical studies
would be needed to decipher the exact reaction mechanism.
substituted
spirocyclopentanone 3x with diminished enantiomeric excess.
Pleasantly, 1-(3,4-dihydro-2H-pyran-6-yl)cyclobutan-1-ol
vinylcyclobutanol
was
converted
to
participated in this asymmetric arylative rearrangement
process to provide 3y in 63% yield with 95% ee (d.r. >20:1) by
employing L7 as the ligand for this reaction.
O
HO
CuCl (0.1 equiv )
L8 (0.15 equiv)
AsF6
Mes
n
n
Ar
I
+
DTBP (2.0 equiv)
DCM, RT
n = 1, 2
Ar
Ar = Ph or 4-BrC6H4
1
2
3
O
O
O
Br
Br
Br
O
Ph
76%, 4.2:1 d.r.
AsF6
Mes
ClCu(I)L*
3t
3u
3v
Ar
I
Ar
A
84%, 6.5:1 d.r.
94% ee (94% ee)
88%, 6.0:1 d.r.
94% ee (94% ee)
Ph
Ph
95% ee (92% ee)
2
3 (major)
O
O
O
Ar
Cl
N
O
Ar
O
Cu+(III)L*
AsF6
N
MeO
MeO
O
Cu
B
Br
O
Ph
Ph
Ph
OH
D
Ph
Ph
voie a
Me
3y
3w
3x
Ar
O
voie b
63%, >20:1 d.r.
63%, >20:1 d.r.
O
70%, >20:1 d.r.
72% ee
Ar
Cu
H
N
94% ee[a]
95% ee[b]
N
1a
O
E
O
Ph
Ph
Scheme 4. Scope of the allylic alcohols. [a] At 50 oC. [b] Cu(OTf)2 (0.1
equiv) as the catalyst and L7 (0.15 equiv) as the ligand at 60 oC.
voie c
C
Ph
Ph
Ar
O
O
N
N
O
Cu
Ar
CuCl (0.1 equiv)
L8 (0.15 equiv )
O
OTMS
+
ClCu(I)L*
O
Ph
F
Ph
AsF6
eq 1
eq 2
3 (major)
Ph
I
Mes
Ph
A
DTBP (2.0 equiv)
DCM, RT
4
5
2a
3a trace
O
Scheme 6. Possible reaction pathway.
Cu(OTf)2 (0.1 equiv)
L8 (0.15 equiv )
Ph
HO
AsF6
CuCl (0.1 equiv)
L8 (0.15 equiv )
Ph
O
O
+
Ph
I
Mes
Bn
6 58%, 31% ee
AsF6
Mes
DTBP (2.0 equiv)
DCM, RT
1
1
+
1a
Ar
I
+
Ar
2
Ar
2a
2
DTBP (2.0 equiv)
DCM, RT
3.0 mmol 3.9 mmol
(1R,2S)-3d
67%, 95% ee
(1S,2S)-3d
17%, 95% ee
Scheme 5. Control experiments.
Ar = 4-Cl-C6H4
O
O
HO
mCPBA (3.0 equiv)
NaHCO3 (4.0 equiv )
Red-Al
Ar
A series of control experiments were carried out in order to
investigate the mechanism of this enantioselective arylative
semipinacol rearrangement (Scheme 5). Only a trace amount
of 3a was observed when TMS-protected vinylcyclobutanol 4
was employed as a substrate indicating the importance of the
free hydroxyl group in this transformation (eq 1).[10a,b]
CHCl3, RT, 48 h
toluene, 0 o
C
Ar
8 45%, 94% ee
7 99%, >20:1 d.r., 94% ee
Scheme 7. Scale-up reaction and synthetic transformations of (1R,2S)-3d.
Importantly, vinylcyclobutanol without indene moiety
5
Reaction of allylic alcohol 1a with 4-Cl-substituted
diaryliodonium salt on a 3.0 mmol scale proceeded smoothly to
afford (1R,2S)-3d (95% ee) and (1S,2S)-3d (95% ee) in yields
of 67% and 17%, respectively (Scheme 7). Reduction of
(1R,2S)-3d with Red-Al afforded alcohol 7 in >99% yield (>
underwent this domino transformation to afford the desired
product 6 in 58% yield with a noticeable ee of 31%. Since the
phenylation of terminal double bond of 5 did not generate a
stereocenter, the observed enantioselectivity can only be
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10.1002/chem.201703563
Chemistry - A European Journal
COMMUNICATION
[8]
[9]
S. J. Kwon, D. Y. Kim, Org. Lett. 2016, 18, 4562.
20:1 d.r., 94% ee), while the Baeyer-Villiger oxidation of
(1R,2S)-3d (mCPBA, NaHCO3, CHCl3, RT) afforded the
desired lactone 8 in 45% yield with 94% ee.
a) A. Pinto, Y. Jia, L. Neuville, J. Zhu, Chem. Eur. J. 2007, 13, 961; b)
W. Kong, Q. Wang, J. Zhu, J. Am. Chem. Soc. 2015, 137, 16028; c)
W. Kong, Q. Wang, J. Zhu, Angew. Chem. Int. Ed. 2016, 55, 9714;
Angew. Chem. 2016, 128, 9866; d) W. Kong, Q. Wang, J. Zhu,
Angew. Chem. 2017, 129, 4045; Angew. Chem. Int. Ed. 2016, 55,
3987; e) X. Bao, Q. Wang, J. Zhu, Angew. Chem. Int. Ed. 2017, DOI:
In summary, we developed an efficeint copper-catalyzed
enantioselective arylative semipinacol rearrangement of allylic
alcohols with diaryliodonium salts. While excellent
enantioselectivity was observed for most of the substrate, the
diastereoselectivity of the reaction was found to be substrate
depending. In general, spiro[4,4]nonanes were formed with
moderate d.r., whereas excellent diastereoselectivities (>20:1
d.r.) were observed with the formation of spiro[4,5]decanes.
10.1002/anie.201705641;
Angew.
Chem.
2017,
DOI:
10.1002/ange.201705641.
[10] Amide-directed enantioselective arylation of alkenes with
diaryliodonium salts catalyzed by copper complex, see: a) A. Bigot, A.
E. Williamson, M. Gaunt, J. Am. Chem. Soc. 2011, 133, 13778; b) J.
S. Harvey, S. P. Simonovich, C. R. Jamison, D. W. C. MacMillan, J.
Am. Chem. Soc. 2011, 133, 13782; c) S.-L. Zhu, D. W. C. MacMillan,
J. Am. Chem. Soc. 2012, 134, 10815; d) E. Cahard, H. P. J. Male, M.
Tissot, M. Gaunt, J. Am. Chem. Soc. 2015, 137, 7986; e) C. Liu, J.-C.
Yi, X.-W. Liang, R.-Q. Xu, L.-X. Dai, S.-L. You, Chem. Eur. J. 2016,
22, 10813. For diastereoselective arylation, see: M. E. Kieffer, K. V.
Chuang, S. E. Reisman, J. Am. Chem. Soc. 2013, 135, 5557.
[11] D. H. Lukamto, M. J. Gaunt, J. Am. Chem. Soc. 2017, DOI:
10.1021/jacs.7b05340.
Acknowledgements
Financial supports from EPFL (Switzerland) and Swiss
National Science Foundation (SNSF) are gratefully
acknowledged. We thank Dr. F.-T. Farzaneh and Dr. R.
Scopelliti for X-ray crystallographic analysis of (1S,2S)-3a.
[12] Recent enantioselective synthesis, see: a) L. Fan, S. Takizawa, Y.
Takeuchi, K. Takenaka, H. Sasai, Org. Biomol. Chem. 2015, 13,
4837; b) B. F. Rahemtulla, H. F. Clark, M. D. Smith, Angew. Chem.
Int. Ed. 2016, 55, 13180; Angew. Chem. 2016, 128, 13374.
[13] J.-H. Xie, Q.-L. Zhou, Acc. Chem. Res. 2008, 41, 581.
[14] M. G. Palermo, G. J. O’Malley, WO1997037992 A2.
[15] CCDC 1533655 [(1S,2S)-3a] contains the supplementary
crystallographic data for this paper. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via www.
ccdc.cam.ac.uk/data_request/cif.
Keywords: semipinacol rearrangement • Ring expansion •
diaryliodonium salt • homogeneous catalyst • Asymmetric
catalysis
[1]
[2]
a) For reviews, see: T. J. Snape, Chem. Soc. Rev. 2007, 36, 1823; b)
B. Wang, Y.-Q. Tu, Acc. Chem. Res. 2011, 44, 1207; c) S.-H. Wang,
B.-S. Li, Y.-Q. Tu, Chem. Commun. 2014, 50, 2393.
[16] B. Chen, X.-L. Hou, Y.-X. Li, Y.-D. Wu, J. Am. Chem. Soc. 2011, 133,
7668.
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10.1002/chem.201703563
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
Asymmetric Synthesis
O
L* =
HO
R'
R
Ar
Cu
O
O
O
L
AsF6
Mes
R
CuCl, L*
R
*
Hua Wu, Qian Wang, and Jieping
Zhu*__________ Page – Page
n
Ph
Ph
n
+
Ar
I
L
N
N
R'
n = 1, 2
R'
Ar
Ph
Ph
n
Copper-Catalyzed Enantioselective
Domino Arylation/Semipinacol
Rearrangement of Allylic Alcohols with
Diaryliodonium Salts
Selective arylation and shift: Copper-catalyzed enantioselective arylative semipinacol rearrangement
of allylic alcohols with diaryliodonium salts afforded spirocycloalkanones in good to high yields with
high diastereo- and enantioselectivities.
This article is protected by copyright. All rights reserved.