Tandem gold-catalyzed hydrosilyloxylation-aldol and -Mannich reaction with alkynylaryloxysilanols in 6-exo mode

Article abstract of DOI:10.1002/adsc.201300244

The tandem gold-catalyzed hydrosilyloxylation-aldol and hydrosilyloxylation-Mannich reactions were developed through the formation of an enol silyl ether catalytically generated in situ from alkynylaryloxysilanols in the 6-exo mode in one reaction vessel. Copyright

Full text of DOI:10.1002/adsc.201300244

FULL PAPERS
DOI: 10.1002/adsc.201300244
Tandem Gold-Catalyzed Hydrosilyloxylation–Aldol and
–Mannich Reaction with Alkynylaryloxysilanols in 6-exo Mode
Euichul Lee,a Taekyu Ryu,a Youngchul Park,a Sangjune Park,a and Phil Ho Leea,*
a
Department of Chemistry, Kangwon National University, Chuncheon 200-701, Republic of Korea
Fax : (+82)-33-253-7582; e-mail: phlee@kangwon.ac.kr
Received: March 24, 2013; Revised: April 12, 2013; Published online: May 15, 2013
Dedicated to Professor Junghun Suh on the occasion of his honorable retirement from Seoul National Universi-
ty.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300244.
Abstract: The tandem gold-catalyzed hydrosilyloxy- kynylaryloxysilanols in the 6-exo mode in one reac-
lation–aldol and hydrosilyloxylation–Mannich reac- tion vessel.
tions were developed through the formation of an
enol silyl ether catalytically generated in situ from al- Keywords: aldol reaction; 6-exo mode; gold; hydrosi-
lyloxylation; Mannich reaction
Introduction
Results and Discussion
Aldol[1] and Mannich reactions[2] rely on the activa- First, a variety of functionalized alkynylaryloxysila-
tion of carbonyl compounds by transforming them nols 1 was prepared by Sonogashira coupling reaction
into enolates or their derivatives. These moieties have of 2-iodophenol derivatives with alkynes and a semi-
been synthesized from the carbonyl compounds by one-pot reaction of alkynylphenols with di-tert-butyl-
deprotonation with bases or deprotonation–enolate chlorosilane followed by bromination and hydrolysis
trap with electrophiles.[1] However, because sensitive (Scheme 2).[6] However, chlorodiisopropylsilane and
functional groups are not tolerated under these condi- chlorodiphenylsilane gave the desired silanes in low
tions, enolates or enol derivatives must be synthesized yield.
separately in advance of the addition of electrophiles
Our investigation started with 1a (Table 1). In gen-
in the following step, indicating that the selective eral, Au catalysts activate effectively C-C multiple
preparation of an enolate from another precursor in bonds and Ag salts increase the catalytic activity of
lieu of a carbonyl compounds is very important. Thus, Au catalysts. On the basis of these results, we used an
we have tried to develop synthetic methods for enol Au/Ag catalytic system for cyclization. When 1a was
derivatives from easily accessible non-carbonyl pre- treated with Ph3PAuCl (5 mol%) in the presence of
cursors.[3] A wide range of synthetic methods of eno- AgAsF6, AgSbF6, or AgBF4 (5 mol% each) in DCE,
lates from non-carbonyl compounds has been report- the hydrosilyloxylation reaction did not proceed (en-
ed to date.[4] Recently, we reported the gold-catalyzed tries 1–3). Although the use of Ph3PAuCl and AgPF6
hydrophosphoryloxylation to alkynes, which produced (5 mol% each) produced the desired enol silyl ether
enol phosphates.[3c,d] Inspired by a variety of efficient 2a in 37% yield in DCE at 808C after 16 h, benzyl 2-
catalytic cyclizations[4e,5] between alkynes and tether- hydroxyphenyl ketone (3) was present as contamina-
ing nucleophiles and gold-catalyzed hydrosilyloxyla- tion in 20% yield (entry 4). AgOTf as a non-coordi-
tion via the 6-endo mode,[3e] we hypothesized that an nating counterion of the cationic gold(I) catalyst ac-
alkynylaryloxysilanol may serve as precursor of the celerated the cyclization. Under thess conditions, the
enol silyl ether via the 6-exo mode driving aldol and cyclized product 2a was obtained in 45% yield after
Mannich reactions (Scheme 1).
1 h (entry 6). The more electrophilic Au catalyst de-
rived from (C6F5)3PAuCl gave a better result (63%
yield) than Ph3PAuCl in the presence of AgOTf
(entry 7). However, formation of 3 (19%) was inevita-
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Scheme 1. Catalytic hydrosilyloxylation via 6-exo mode driving the aldol and Mannich reactions.
Scheme 2. Preparation of alkynylaryloxysilanols.
Table 1. Optimization of the intramolecular hydrosilyloxylation.[a]
Entry
Cat.[a]
Solvent
T [oC]
t [h]
Yield [%][b]
1
2
3
4
5
6
7
8
Ph3PAuCl/AgAsF6
Ph3PAuCl/AgSbF6
Ph3PAuCl/AgBF4
Ph3PAuCl/AgPF6
Ph3PAuCl/AgNTf2
Ph3PAuCl/AgOTf
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
CH3NO2
dioxane
DCE
DCE
DCE
80
80
80
80
80
80
80
80
25
100
100
40
25
80
16
16
16
16
5
1
2
3
6
16
16
1
1
5
0
0
0
37 (20)
31
45
63 (19)
83
0
A
(4-CF3-C6H4)3PAuCl/AgOTf
(4-CF3-C6H4)3PAuCl/AgOTf
(4-CF3-C6H4)3PAuCl/AgOTf
(4-CF3-C6H4)3PAuCl/AgOTf
AuCl3/AgOTf[c]
9
10
11
12
13
14
0
0
53 (29)
20 (35)
18 (39)
TfOH
AgOTf
[a]
Au and Ag (5 mol% each) were used.
Numbers in parenthesis are yields of benzyl 2-hydroxyphenyl ketone (3).
15 mol% Ag were used.
[b]
[c]
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Tandem Gold-Catalyzed Hydrosilyloxylation–Aldol and –Mannich Reaction with Alkynylaryloxysilanols
80% yield in DCE at 808C after 3 h. 4-Chlorophenyl-
and 4-trifluoromethylphenyl-substituted alkynylaryl-
AHCTUNGTREGUNoNN xysilanols 1c and 1d were cyclized to produce enol
silyl ethers 2c (73%) and 2d (73%). A methyl group
on the phenyl ring possessing silyloxy and alkynyl
groups impacted somewhat on the cyclization effec-
tiveness and, thus, the desired enol silyl ether 2e was
obtained in 53% yield. Silanols 1f and 1g possessing
aliphatic alkynyl groups were smoothly converted to
enol silyl ethers 2f (86%) and 2g (83%). A chloride
group is tolerated in the Au-catalyzed hydrosilyloxy-
lation reaction. Because enol silyl ethers obtained
from aliphatic alkynylaryloxysilanols were unstable,
the corresponding yields were determined by
1H NMR using dibromomethane as an internal stan-
dard.
Encouraged by these results, we attempted the
tandem gold-catalyzed hydrosilyloxylation–aldol reac-
tion that tolerates both the catalytic generation of the
enol silyl ether and the subsequent aldol reaction in
one reaction vessel. However, 1a did not react with
butyraldehyde in the presence of gold catalyst
(entry 1, Table 2), indicating that silyl enol ether 2 de-
rived from the alkynylaryloxysilanol was less reactive
than the one derived from alkynylarylsilanol because
two oxygens were tethered to silicon. Consequently,
Table 2. Lewis acid screening for the Mukaiyama aldol
reaction.[a]
Scheme 3. Gold-catalyzed intramolecular hydrosilyloxyla-
tion.
Entry
Lewis acid
–
t [h]
Yield [%]
1
2
3
4
5
6
12
12
12
12
12
12
6
6
6
6
(75)[b]
ble. The best result was obtained by using (4-CF3-
C6H4)3PAuCl and AgOTf (5 mol% each) in DCE at
808C after 3 h, which gratifyingly gave rise to 2a in
83% yield via a selective 6-exo mode (entry 8). No
enol silyl ether via a 6-endo mode is formed. NOE ex-
periments indicate that stereochemistry of 2a is the Z
form. However, the reaction did not proceed in nitro-
methane and 1,4-dioxane (entries 10 and 11). AuCl3
was inferior to (4-CF3-C6H4)3PAuCl (entry 8 vs. 12).
To check the possibility of catalysis by a protic acid,
we attempted the hydrosilyloxylation in the presence
of TfOH (5 mol%), which produced 2a (20%) and 3
(35%) (entry 13). AgOTf alone was ineffective for
the cyclization (entry 14).
Sc
N
0
TMSOTf
InI3
ZnCl2
(68)[b]
(65)[b]
(64)[b]
Zn
N
(68)[b]
7[c,d]
8[c,g]
9[c,h]
10[c]
BF3·OEt2
BF3·OEt2
BF3·OEt2
BF3·OEt2
52[e] (16)[f]
45[e] (24)[f]
45[e] (24)[f]
67[e] (9)[f]
[a]
Au, Ag (5 mol% each), Lewis acid (1 equiv.), silanol
(1 equiv.) and n-PrCHO (2 equiv.).
Isolated yield of 2a.
n-PrCHO and BF3·OEt2 in DCM at À788C were added
to the reaction mixture cooled to À788C in DCE and
DCM.
n-PrCHO (1 equiv.).
Diastereomeric ratio=1:2.8.
Isolated yield of 3.
n-PrCHO (1.5 equiv.) and BF3·OEt2 (1.5 equiv.).
[b]
[c]
Next, we examined diverse alkynylaryloxysilanols
for the intramolecular hydrosilyloxylation (Scheme 3).
Reaction of 1b having an electron-donating methyl
group on the phenyl ring with (4-CF3-C6H4)3PAuCl
and AgOTf (5 mol% each) gave enol silyl ether 2b in
[d]
[e]
[f]
[g]
[h]
n-PrCHO (2 equiv.) and BF3·OEt2 (2 equiv.).
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a variety of Lewis acids was examined to activate al-
dehyde in the Mukaiyama aldol reaction. However,
the use of Sc
ACHTUNGTRENNUNG(OTf)3, TMSOTf, InI3, ZnCl2, and
Zn(OTf)2 (1 equiv. each) did not afford the desired
ACHTUNGTRENNUNG
aldol product 4a (entries 2–6).[7] When BF3·OEt2 was
used as a Lewis acid, the yield of product (4a) and
side product (3) was sensitive to the stoichiometry of
butyraldehyde and BF3·OEt2. When butyraldehyde
(2 equiv.) and BF3·OEt2 (1 equiv.) in DCM at À788C
were added to the reaction mixture cooled to À788C
in DCE and DCM, the best result was obtained.
Under these conditions, aldol adduct 4a was produced
in 67% yield (dr=1:2.8) via the intramolecular hydro-
silyloxylation in a selective 6-exo mode followed by
an aldol reaction in one reaction vessel along with 3
in 9% yield (entry 10). The use of butyraldehyde in
less than 2 equiv. and BF3·OEt2 in more than 1 equiv.
gave lower yields (entries 7–9).
As expected, when enol silyl ether 2a was treated
with butyraldehyde in the presence of (4-CF3-
C6H4)3PAuCl and AgOTf (5 mol% each), the aldol
product was not obtained [Eq. (1)]. This result indi-
cates that gold plays a catalytic role in only the hydro-
silyloxylation step. In addition, treatment of 2a with
butyraldehyde in the presence of BF3·OEt2 provided
the desired aldol product 4a in 83% yield (dr=1:2.6)
in DCM at À788C after 6 h [Eq. (2)].
Scheme 4. Tandem hydrosilyloxylation–Mukaiyama aldol re-
action.[a]
Having successfully established the tandem hydrosi-
lyloxylation–aldol reactions, we then studied the
tandem gold-catalyzed intramolecular hydrosilyloxyla-
tion–Mannich reaction starting from enol silyl ether
and imine. Treatment of 2a with 5 (1.2 equiv.) gave
the desired 6a in 69% yield (dr=1:2.3) in the pres-
Under the optimized reaction conditions, various ence of BF3·OEt2 in dichloromethane at À788C after
alkynylaryloxysilanols were examined in one reaction 6 h [Eq. (3)].
vessel (Scheme 4). Phenoxysilanols 1b and 1c having
4-methylphenylethynyl
or
4-chlorophenylethynyl
groups underwent the gold-catalyzed hydrosilyloxyla-
tion and sequential BF3·OEt2-mediated aldol reaction
with butyradehyde to provide aldol products 4b
(65%, dr=1:2.1) and 4c (53%, dr=1:1.1) in one reac-
tion vessel. Under the optimized reaction conditions,
1-hexyn-1-yl- and 5-phenyl-1-pentyn-1-yl-substituted
phenoxysilanols 1f and 1g were also successfully sub-
jected to the tandem intramolecular hydrosilyloxyla-
In addition, we explored the gold-catalyzed tandem
tion and aldol reaction with butyraldehyde, affording intramolecular hydrosilyloxylation–Mannich reaction
the desired aldol products 4f (65%, dr=1:1.3) and 4g of alkynylaryloxysilanol with 5 in one reaction vessel
(40%, dr=1:1.3) in one-pot. When a tandem reaction (Scheme 5). Silanols 1a and 1b having phenylethynyl
was carried out with 1h and butyraldehyde, the de- and
4-methylphenylethynyl
groups
underwent
sired aldol compound 4h was isolated in 53% yield a smooth gold-catalyzed tandem hydrosilyloxylation–
(dr=1:1.8), indicating that a chloride group is tolerat- Mannich reaction to provide 6a (53%, dr=1:2.4) and
ed in the present reaction.
6b (52%, dr=1:2.8), respectively. Enol silyl ether 2f
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Tandem Gold-Catalyzed Hydrosilyloxylation–Aldol and –Mannich Reaction with Alkynylaryloxysilanols
ysilanols without the use of bases, which opens new
opportunities for the invention of related transition
metal- and Lewis acid-catalyzed processes.
Experimental Section
General Methods
Reactions were carried out in oven-dried glassware under
a nitrogen atmosphere. Commercial reagents were pur-
chased and were used without purification, and all solvents
were reaction grade. Dichloroethane (DCE) was freshly dis-
tilled from calcium hydride. All reaction mixtures were
stirred magnetically and were monitored by thin-layer chro-
matography using silica gel precoated glass plates, which
were visualized with UV light and then developed using a so-
lution of p-anisaldehyde. Flash column chromatography was
carried out using silica gel (230–400 mesh). 1H NMR and
13C NMR spectra were recorded on 300 and 400 MHz spec-
trometers. Deuterated chloroform was used as the solvent.
The chemical shift values (d) are reported in parts per mil-
lion relative to the residual signals of solvent (CDCl3: d=
Scheme 5. Tandem hydrosilyloxylation–Mannich reaction.[a]
generated in situ from the treatment of 1f possessing
a 1-hexyn-1-yl group with gold catalyst was sequen-
tially subjected to 5 (1 equiv.) at À788C to furnish 6f
in 53% (dr=1:2.8) via a tandem hydrosilyloxyaltion–
Mannich reaction in one-pot.
Finally, treatment of 4a-major with tetrabutylam-
monium fluoride (TBAF) in THF at 08C produced 7
in 94% yield [Eq. (4)]. In addition, exposure of 6a-
major to TBAF resulted in 8 in 81% yield in THF at
À788C [Eq. (5)].
1
7.26 for H and d=77.16 for 13C). Infrared spectra were re-
corded on an FT-IR spectrometer as a thin film pressed be-
tween two sodium chloride plates. Mass spectrometry was
performed on a GC/HR-MS spectrometer (KBSI) under
electron impact (EI) ionization technique (magnetic sector-
electric sector double focusing mass analyzer). Melting
points were determined in open capillary tube.
Typical Experimental Procedures for Synthesis of Di-
tert-butyl[2-(phenylethynyl)phenoxy]silanol
To a solution of PdCl2ACHTNUTRGNE(UGN PPh3)2 (70.2 mg, 0.1 mmol, 2 mol%)
and CuI (38.1 mg, 0.2 mmol, 4 mol%) in THF (15.0 mL)
were added Et3N (1.05 mL, 7.5 mmol), 2-iodophenol (1.0 g,
5.0 mmol), and phenylacetylene (577.0 mL, 5.25 mmol) at
08C. The dark brown mixture was stirred at room tempera-
ture for 5 h. The reaction mixture was quenched with water
(20 mL). The aqueous layer was extracted with diethyl ether
(3ꢁ20 mL), and the organic layer was washed with brine
(20 mL), dried over MgSO4, and concentrated under re-
duced pressure. Silica gel flash column chromatography
(EtOAc: hexane=1:10) gave 2-(phenylethynyl)phenol A as
yellow oil;[8] yield: 815.8 mg (4.2 mmol, 84%).
To a solution of A (815.8 mg, 4.2 mmol) in CH2Cl2
(8.4 mL) were added triethylamine (643.9 mL, 4.6 mmol),
DMAP (48.9 mg, 0.4 mmol) and di-tert-butylchlorosilane
(934.3 mL, 4.6 mmol). After the solution had been stirred at
room temperature for 2 h, hexane (40 mL) was added and
the mixture filtered. The filtrate was concentrated under re-
duced pressure. To this crude mixture, hexane (40 mL) was
added and the whole filtered again, and concentrated to
give the corresponding silane. This silane in dichlorome-
thane (5 mL) was added to NBS (818.7 mg, 4.6 mmol) in di-
chloromethane (5 mL). After the resulting mixture had been
stirred for 3 h, DMF (1.0 mL) and aqueous NaOH (1 mL,
1 N) were added and the mixture stirred at room tempera-
ture for 2 h. Upon completion (judged by TLC), the mixture
was concentrated under reduced pressure. Water (10 mL)
Conclusions
In conclusion, we have developed efficient tandem
gold-catalyzed hydrosilyloxylation/Mukaiyama aldol
reaction and hydrosilyloxylation/Mannich reaction via
the formation of enol silyl ether catalytically generat-
ed in situ from readily available alkynylaryloxysilanols
in a selective 6-exo mode in one reaction vessel. Key
to the success of these tandem reactions is the selec-
tive formation of enol silyl ethers from alkynylarylox- was added and the mixture extracted with ether (3ꢁ20 mL),
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Euichul Lee et al.
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dried over MgSO4 and evaporated. Silica gel flash column
chromatography (EtOAc:hexane=1:10) gave di-tert-butyl(2-
(phenylethynyl)phenoxy)silanol 1a as a yellow oil;[9] yield:
1.4 g (4.1 mmol, 98%)
1455, 751, 439 cmÀ1; HR-MS (EI): m/z=174.1043, calcd. for
C12H14O: 174.1045.
2-(5-Phenylpent-1-yn-1-yl)phenol (G): yield; 731 mg
1
(62%); Rf =0.3 (EtOAc:hexane=1:15); yellow oil. H NMR
(400 MHz, CDCl3): d=7.32–7.29 (m, 3H), 7.22–7.19 (m,
4H), 6.93 (dd, J=8.2, 0.9 Hz, 1H), 6.85 (td, J=7.5, 1.1 Hz,
1H), 5.77 (s, 1H), 2.79 (t, J=15.0 Hz, 2H), 2.49 (t, J=
7.0 Hz, 2H), 1.97 (quintet, J=7.3 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=156.5, 141.2, 131.5, 129.7, 128.5,
128.4, 126.0, 120.2, 114.3, 110.1, 97.4, 75.0, 34.8, 30.2, 19.0;
IR (film): n=3500, 3025, 2940, 1485, 1235, 753, 700,
438 cmÀ1; HR-MS (EI): m/z=236.1201, calcd. for C17H16O:
236.1201.
2-(Phenylethynyl)phenol (A):yield: 835 mg (86% ); Rf =
1
0.4 (EtOAc:hexane=1:10); yellow oil. H NMR (400 MHz,
CDCl3): d=7.57–7.52 (m, 2H), 7.42 (dd, J=7.7, 1.4 Hz,
1H), 7.39–7.36 (m, 3H), 7.29–7.24 (m, 1H), 6.99 (dd, J=8.2,
0.8 Hz, 1H), 6.91 (td, J=7.5, 1.1 Hz, 1H), 5.83 (s, 1H);
13C NMR (100 MHz, CDCl3): d=156.5, 131,67, 131.62,
130.5, 128.8, 128.5, 122.3, 120.4, 114.7, 109.5, 96.4, 83.0; IR
(film): n=3509, 3061, 1495, 1479, 752, 689, 426 cmÀ1; HR-
MS (EI): m/z=194.0733, calcd. for C14H10O: 194.0732.
2-(p-Tolylethynyl)phenol (B): yield: 728 mg (70%); Rf =
0.3 (EtOAc:hexane=1:15); pale yellow solid; mp 85–898C.
1H NMR (400 MHz, CDCl3): d=7.44–7.40 (m, 2H), 7.27–
7.24 (m, 1H), 7.18 (dd, J=8.4, 0.5 Hz, 2H), 6.97 (dd, J=8.3,
0.7 Hz, 1H), 6.90 (td, J=7.5, 1.1 Hz, 1H), 5.84 (s, 1H), 2.38
(s, 3H); 13C NMR (100 MHz, CDCl3): d=156.4, 139.1,
131,58, 131.52, 130.3, 129.2, 120.4, 119.2, 114.6, 109.7, 96.6,
82.3, 21.5; IR (film): n=3434, 3031, 1512, 1484, 817, 745,
426 cmÀ1; HR-MS (EI): m/z=208.0812, calcd. for C15H12O:
208.0888.
2-[(4-Chlorophenyl)ethynyl]phenol (C): yield: 983 mg
(86%); Rf =0.3 (EtOAc:hexane=1:15), white solid; mp 65–
738C. 1H NMR (400 MHz, CDCl3): d=7.47 (dt, J=8.8,
2.0 Hz, 2H), 7.41 (dd, J=7.7, 1.5 Hz, 1H), 7.35 (dt, J=8.6,
1.9 Hz, 2H), 7.30–7.26 (m, 2H), 6.98 (dd, J=8.2, 0.6 Hz,
1H), 6.92 (td, J=7.5, 1.0 Hz, 1H), 5.76 (s, 1H); 13C NMR
(100 MHz, CDCl3): d=156.5, 134.9, 132.8, 131.7, 130.7,
128.8, 120.8, 120.5, 114.8, 109.2, 95.1, 84.0; IR (film): n=
3416, 1494, 1478, 1199, 1180, 828, 754, 426 cmÀ1; HR-MS
(EI): m/z=228.0345, calcd. for C14H9ClO: 228.0342.
2-(5-Phenylpent-1-yn-1-yl)phenol (H): yield: 699 mg
1
(72%); Rf =0.4 (EtOAc:hexane=1:15); yellow oil. H NMR
(400 MHz, CDCl3): d=7.30 (dd, J=7.6, 1.6 Hz, 1H), 7.24–
7.20 (m, 1H), 6.93 (dd, J=8.2, 1.0 Hz, 1H), 6.85 (td, J=7.5,
1.1 Hz, 1H), 3.72 (t, J=6.2 Hz, 2H), 2.70 (t, J=6.8 Hz, 2H),
2.09 (quintet, J=6.6 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=156.6, 131.5, 129.9, 120.2, 114.4, 109.7, 95.5, 75.6, 43.6,
31.2, 17.0; IR (film): n=3498, 2842, 1486, 1290, 1235, 744,
439 cmÀ1
;
HR-MS (EI): m/z=194.0500, calcd. for
C11H11ClO: 194.0498.
Di-tert-butyl[2-(phenylethynyl)phenoxy]silanol
(1a):
yield: 1.4 g (98%); Rf =0.3 (EtOAc:hexane=1:10); yellow
oil. 1H NMR (400 MHz, CDCl3): d=7.52–7.46 (m, 3H),
7.37–7.31 (m, 2H), 7.20 (td, J=7.7, 1.6 Hz, 1H), 7.13 (dd,
J=8.2, 1.1 Hz, 1H), 6.93 (td, J=7.4, 1.2 Hz, 1H), 2.53
ACHTUNGTRENNUNG(s,
1H), 1.11
AHCTUNGTRENNUNG
131.8, 130.0, 128.7, 128.5, 123.9, 121.5, 120.1, 115.0, 93.3,
87.5, 27.7, 21.1; IR (film): n=3647, 3062, 3032, 2934, 2859,
1469, 1481, 1289, 1247, 930, 829 cmÀ1. HR-MS (EI): m/z=
352.1862, calcd. for C22H28O2Si: 352.1859.
Di-tert-butyl[2-(p-tolylethynyl)phenoxy]silanol
(1b):
2-{[4-(Trifluoromethyl)phenyl]ethynyl}phenol (D): yield:
733 mg, (56%); Rf =0.3 (EtOAc:hexane=1:15); brown
solid; mp 75–788C. 1H NMR (400 MHz, CDCl3): d=7.71–
7.61 (m, 4H), 7.44 (dd, J=7.6, 1.6 Hz, 1H), 7.33–7.28 (m,
1H), 6.99 (dd, J=8.3, 0.6 Hz, 1H), 6.93 (td, J=11.3, 1.0 Hz,
1H), 5.75 (s, 1H); 13C NMR (100 MHz, CDCl3): d=156.6,
131.9, 131.8, 131.6, 131.1, 126.2, 125.4 (d, J=3.6 Hz), 120.6,
115.0, 108.9, 99.4, 85.5, 77.2; 19F NMR (376 MHz, CDCl3):
d=À62.8; IR (film): n=3509, 2928, 1324, 1129, 1105, 839,
yield: 1.2 g (94%); Rf =0.3 (EtOAc:hexane=1:10); pale
yellow solid; mp 40–458C. H NMR (400 MHz, CDCl3): d=
1
7.46 (dd, J=7.6, 1.6 Hz, 1H), 7.40 (dt, J=7.9, 7.6 Hz, 2H),
7.21–7.10 (m, 4H), 6.92 (td, J=7.4, 1.2 Hz, 1H), 2.57 (s,
1H), 2.36 (s, 3H), 1.11 (s, 18H); 13C NMR (100 MHz;
CDCl3): d=156.4, 133.5, 131.3, 129.4, 129.1, 121.1, 120.4,
119.8, 114.7, 93.0, 86.4, 77.2, 27.3, 21.5, 20.7; IR (film): n=
3643, 2965, 2934, 2858, 1485, 1445, 1288, 1247, 931, 829 cmÀ1
;
HR-MS (EI): m/z=366.2014, calcd. for C23H30O2Si:
366.2015.
754, 438 cmÀ1
; HR-MS (EI): m/z=262.0605, calcd. for
C15H9F3O: 262.0605.
Di-tert-butyl{2-[(4-chlorophenyl)ethynyl]phenoxy}silanol
(1c): yield: 1.4 g (83%); Rf =0.3 (EtOAc:hexane=1:10);
yellow oil. 1H NMR (400 MHz, CDCl3): d=7.47–7.41 (m,
3H), 7.31 (dt, J=8.9, 2.1 Hz, 2H), 7.24–7.19 (m, 1H), 7.14
(dd„ J=8.3, 1.0 Hz, 1H), 6.93 (td, J=7.4, 1.2Hz, 1H), 2.48
(s, 1H), 1.10 (s, 18H); 13C NMR (100 MHz, CDCl3): d=
156.6, 134.0, 133.4, 132.6, 129.8, 128.7, 122.0, 121.1, 119.6,
114.2, 91.7, 88.0, 27.3, 20.7; IR (film): n=3590, 3069, 2934,
2892, 1495, 1482, 1289, 1248, 932, 828 cmÀ1; HR-MS (EI):
m/z=387.1544, calcd. for C22H27ClO2Si: 387.1547.
4-Methyl-2-(phenylethynyl)phenol (E): yield: 791 mg
(76%); Rf =0.4 (EtOAc:hexane=1:10); brown solid; mp
65–738C. 1H NMR (400 MHz, CDCl3): d=7.54–7.50 (m,
2H), 7.37–7.33 (m, 2H), 7.23–7.22 (m, 1H), 7.07–7.04 (m,
1H), 6.87 (d, J=8.4 Hz, 1H), 5.70 (s, 1H), 2.26 (s, 3H);
13C NMR (100 MHz, CDCl3): d=154.4, 131.7, 131.6, 131.2,
129.6, 128.7, 128.5, 122.5, 114.5, 109.2, 96.0, 83.3, 20.3; IR
(film): n=3518, 2922, 1487, 1282, 1185, 755, 690, 427 cmÀ1
HR-MS (EI): m/z=208.0885, calcd. for C15H12O: 208.0888.
;
2-(Hex-1-yn-1-yl)phenol (F): yield: 766 mg (88%); Rf =
Di-tert-butyl(2-{[4-(trifluoromethyl)phenyl]ethynyl}phen-
oxy)silanol (1d): yield: 1.0 g (86%); Rf =0.3 (EtOAc:hex-
1
0.4 (EtOAc:hexane=1:15); yellow oil. H NMR (400 MHz,
1
CDCl3): d=7.29 (dd, J=7.6, 1.6 Hz, 1H), 7.21–7.17 (m,
1H), 6.93 (dd, J=8.2, 1.0 Hz, 1H), 6.83 (td, J=11.3, 1.1 H,
1H), 2.49 (t, J=7.1 Hz, 2H), 1.65–1.59 (m, 2H), 1.53–1.44
(m, 2H), 0.96 (t, J=7.3 Hz, 3H); 13C NMR (100 MHz,
CDCl3): d=156.4, 131.4, 129.5, 120.1, 114.2, 110.2, 98.0, 74.4,
30.7, 22.0, 19.2, 13.6; IR (film): n=3504, 2957, 2931, 1485,
ane=1:10); yellow oil. H NMR (400 MHz, CDCl3): d=7.60
(s, 4H), 7.48 (dd, J=7.7, 1.7 Hz, 1H), 7.26–7.16 (m, 2H),
6.94 (td, J=11.1, 1.3 Hz, 1H), 2.49 (s, 1H), 1.11 (s, 18H);
13C NMR (100 MHz, CDCl3): d=156.8, 139.3, 133.5, 131.6,
130.2, 127.4, 125.3 (q, J=3.7), 121.1, 119.6, 118.7, 113.9, 91.4,
89.5, 27.3, 20.7; 19F NMR (376 MHz, CDCl3): d À62.7; IR
1590
asc.wiley-vch.de
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1585 – 1596

Tandem Gold-Catalyzed Hydrosilyloxylation–Aldol and –Mannich Reaction with Alkynylaryloxysilanols
(film): n=3687, 3069, 3029, 2935, 2860, 2217, 1487, 1446,
1323, 1290, 1130, 1065, 932, 841 cmÀ1; HR-MS (FAB+):
m/z=421.1808, calcd. for C23H27F3O2Si [M+H]: 421.1811.
Di-tert-butyl[4-methyl-2-(phenylethynyl)phenoxy]silanol
(1e): yield: 1.1 g (79%); Rf =0.3 (EtOAc:hexane=1:15);
pale yellow oil. 1H NMR (400 MHz, CDCl3): d=7.51–7.49
(m, 2H), 7.35–7.31 (m, 3H), 7.29–7.28 (m, 1H), 7.01 (d, J=
0.9 Hz, 2H), 2.55 (s, 1H), 2.27 (s, 3H), 1.10 (s, 18H);
13C NMR (100 MHz, CDCl3): d=154.3, 133.7, 131.4, 130.4,
130.3, 129.2, 128.3, 128.0, 123.5, 119.5, 114.0, 92.5, 87.3, 27.4,
20.7; IR (film): n=3645, 3055, 3031, 2934, 2858, 1498, 1471,
1284, 1248, 943, 908 cmÀ1; HR-MS (EI): m/z=367.2091,
calcd. for C23H30O2Si: 367.2093.
Di-tert-butyl[2-(hex-1-yn-1-yl)phenoxy]silanol (1f): yield:
1.0 g (70%); Rf =0.4 (EtOAc:hexane=1:10); yellow oil.
1H NMR (400 MHz, CDCl3): d=7.34 (dd, J=7.7, 1.7 Hz,
1H), 7.16–7.12 (m, 1H), 7.04 (dd, J=8.2, 1.0 Hz, 1H), 6.86
(td, J=7.5, 1.3 Hz, 1H), 2.65 (s, 1H), 2.42 (t, J=7.1 Hz,
2H), 1.62–1.55 (m, 2H), 1.51–1.42 (m, 2H), 1.09 (s, 18H),
0.93 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
156.8, 133.9, 129.1, 121.4, 120.3, 115.5, 94.4, 78.6, 31.2, 27,7,
22.4, 21.1, 19.7, 14.0; IR (film): n=3686, 3070, 3031, 2934,
2859, 1488, 1444, 1287, 1267, 922, 829 cmÀ1; HR-MS (EI):
m/z=332.2169, calcd. for C20H32O2Si: 332.2172.
solid; mp 65–738C. 1H NMR (400 MHz, CDCl3): d=7.76
(dd, J=8.3, 1.0 Hz, 2H), 7.52 (dd, J=8.1, 1.6 Hz, 1H), 7.35–
7.31 (m, 2H), 7.22–7.15 (m, 2H), 6.94–6.90 (m, 2H), 6.14 (s,
1H), 1.09 (s, 18H); 13C NMR (100 MHz, CDCl3): d=153.4,
148.9, 137.0, 130.3, 128.9, 128.6, 126.5, 126.2, 124.2, 121.6,
120.3, 106.5, 26.8, 21.7; IR (film): 2964, 2934, 1630, 1473,
1455, 1232, 1116, 907, 828 cmÀ1
; HR-MS (EI): m/z=
352.1862, calcd. for C22H28O2Si: 352.1859.
(Z)-2,2-Di-tert-butyl-4-(4-methylbenzylidene)-4H-
benzo[d]ACHTGNUTERN[UNNG 1,3,2]dioxasiline (2b): yield: 88 mg (80%); Rf =0.4
1
(hexane); colorless oil. H NMR (400 MHz, CDCl3): d=7.66
(d, J=8.2 Hz, 2H), 7.51 (dd, J=8.2, 1.5 Hz, 1H), 7.21–7.14
(m, 3H), 6.94–6.90 (m, 2H), 6.11 (s, 1H), 2.35 (s, 3H), 2.17
(s, 1H), 1.09 (s, 18H); 13C NMR (100 MHz, CDCl3): d=
153.3, 148.2, 135.9, 134.2, 130.1, 129.3, 128.8, 126.4, 124.3,
121.5, 120.2, 106.4, 31.3, 26.8, 21.6; IR (film): n=2965, 2860,
1638, 1474, 1459, 1295, 1241, 905, 827 cmÀ1; HR-MS (EI):
m/z=366.2012, calcd. for C23H30O2Si: 366.2015.
(Z)-2,2-Di-tert-butyl-4-(4-chlorobenzylidene)-4H-benzo-
[d]ACHTUNGTNRE[UNNG 1,3,2]dioxasiline (2c): yield: 85 mg (73%); Rf =0.5
1
(hexane); yellow oil. H NMR (400 MHz, CDCl3): d=7.67
(d. J=8.6 Hz, 2H), 7.50 (dd, J=8.2, 1.6 Hz, 1H), 7.29 (dt,
J=8.5, 2.3 Hz, 2H), 7.24–7.19 (m, 1H), 6.95–6.91 (m, 2H),
6.09 (s, 1H), 1.08 (s, 18H); 13C NMR (100 MHz, CDCl3):
d=153.4, 149.4, 135.5, 131.5, 130.54, 130.51, 130.0, 128.7,
126.4, 123.8, 121.7, 120.3, 105.2, 27.7, 26.8, 21.6; IR (film):
n=3031, 2962, 2935, 1632, 1602, 1166, 1116, 935, 909, 844,
Di-tert-butyl[2-(5-phenylpent-1-yn-1-yl)phenoxy]silanol
(1g): yield: 829 mg (68%); Rf =0.3 (EtOAc:hexane=1:10);
1
yellow oil. H NMR (400 MHz, CDCl3): d=7.35 (dd, J=7.6,
827 cmÀ1
;
HR-MS (EI): m/z=386.1468, calcd. for
1.6 Hz, 1H), 7.31–7.27 (m, 2H), 7.22–7.13 (m, 4H), 7.05 (dd,
J=8.2, 1.1 Hz, 1H), 6.87 (td, J=11.1, 1.1 Hz, 1H), 2.77 (t,
J=7.6 Hz, 2H), 2.61 (s, 1H), 2.44 (t, J=7.1 1Hz, 2H), 1.92
(quintet, J=7.3 Hz, 2H), 1.19 (s, 18H); 13C NMR (100 MHz,
CDCl3): d=156.4, 141.5, 133.5, 128.9, 128.5, 128.3, 125.9,
121.0, 119.9, 115.1, 93.4, 78.7, 34.9, 30.2, 27.3, 20.7, 19.1; IR
(film): n=3626, 3063, 3026, 2934, 2858, 1489, 1445, 1288,
1266, 936, 829 cmÀ1; HR-MS (EI): m/z=394.2325, calcd. for
C25H34O2Si: 394.2328.
C22H27ClO2Si: 386.1469.
(Z)-2,2-Di-tert-butyl-4-[4-(trifluoromethyl)benzylidene]-
4H-benzo[d]ACTHUNGTERN[UNNG 1,3,2]dioxasiline (2d): yield: 92 mg (73%); Rf =
1
0.5 (hexane); colorless oil. H NMR (400 MHz, CDCl3) d=
7.84 (d, J=8.4 Hz, 2H), 7.58–7.52 (m, 3H), 7.26–7.22 (m,
1H), 6.97–6.92 (m, 2H), 6.17 (s, 1H), 1.09 (s, 18H);
13C NMR (100 MHz, CDCl3): d=153.2, 150.6, 140.2, 130.6,
128.3, 127.2 (J=32.2 Hz), 126.2, 125.8, 125.1 (J=3.8 Hz),
123.1, 121.4, 120.0, 104.6, 26.4, 21.2; 19F NMR (376 MHz,
CDCl3): d=À155.1; IR (film): n=3067, 3037, 2963, 1632,
1471, 1323, 853, 429 cmÀ1; HR-MS (FAB+): m/z=421.1809,
calcd. for C23H28F3O2Si [M+H]: 421.1811.
Di-tert-butyl[2-(5-chloropent-1-yn-1-yl)phenoxy]silanol
(1h): yield: 953 mg (75%); Rf =0.4 (EtOAc:hexane=1:10);
1
white solid; mp 40–458C. H NMR (400 MHz; CDCl3): d=
7.33 (dd, J=7.6, 1.7 Hz, 1H), 7.15 (td, J=7.7, 1.6 Hz, 1H),
7.06 (dd, J=8.3, 1.1 Hz, 1H), 6.87 (td, J=7.4, 1.1 Hz, 1H),
3.69 (t, J=6.3 Hz, 2H), 2.62 (t, J=6.8 Hz, 2H), 2.52 (s, 1H),
2.08–2.02 (m, 2H), 1.09 (s, 18H); 13C NMR (100 MHz,
CDCl3): d=156.9, 133.9, 129.4, 121.4, 120.1, 115.1, 92.0, 79.4,
44.1, 31.8, 27.7, 21.1, 17.5; IR (film): n=3625, 3070, 2935,
2859, 1595, 1568, 1488, 1444, 1289, 1266, 938, 829 cmÀ1; HR-
MS (EI): m/z=352.1628, calcd. for C19H29ClO2Si: 352.1625.
(Z)-4-Benzylidene-2,2-di-tert-butyl-6-methyl-4H-benzo-
[d]ACHTUNGTNRE[UNNG 1,3,2]dioxasiline (2e): yield: 58 mg (53%); Rf =0.4
1
(hexane); colorless oil. H NMR (400 MHz, CDCl3): d=7.76
(d, J=7.4 Hz, 2H), 7.32 (t, J=7.8 Hz, 3H), 7.20–7.14 (m
1H), 7.00 (dd, J=8.2, 1.8 Hz, 1H), 6.82 (d, J=8.2 Hz, 1H),
6.12 (s, 1H), 2.30 (s, 3H), 1.08 (s, 18H); 13C NMR
(100 MHz, CDCl3): d=150.9, 148.7, 136.7, 130.7, 130.3,
128.5, 128.2, 126.3, 125.7, 123.3, 119.6, 105.8, 26.5, 21.3; IR
(film): n=3020, 2934, 1633, 1485, 1129, 952 cmÀ1; HR-MS
(FAB+): m/z=367.2091, calcd. for C23H30O2Si [M+H]:
367.2093.
Typical Experimental Procedures for Au-Catalyzed
Hydrosilyloxylation
(Z)-2,2-Di-tert-butyl-4-pentylidene-4H-benzo[d]-
To
a suspension of chloroACHTUNTGERNUNG[tris(4-trifluoromethylphenyl)-
AHCTUNGTERNN[GUN 1,3,2]dioxasiline (2f): yield: 86% (NMR); Rf =0.5
phoshine]gold(I) (10.5 mg, 5 mol%) and AgOTf (3.9 mg,
5 mol%) in DCE (0.6 mL) was added di-tert-butyl[2-(phe-
nylethynyl)phenoxy]silanol 1a (105.9 mg, 0.3 mmol) in DCE
(0.6 mL). After being stirred at 808C for 3 h, the reaction
mixture was filtered over celite 545 and washed by CH2Cl2
(3ꢁ2 mL). The solvent was removed under reduced pres-
sure. The crude product was purified by short silica gel flash
column chromatography (hexane) to give (Z)-4-benzyli-
1
(hexane); colorless oil. H NMR (400 MHz, CDCl3): d=7.36
(dd, J=7.8, 1.7 Hz, 1H), 7.15–7.11 (m, 1H), 6.89–6.83 (m,
2H), 5.20 (t, J=7.2 Hz, 1H), 2.28 (q, J=7.2 Hz, 2H), 1.45–
1.38 (m, 4H), 1.06 (s, 18H), 0.93 (t, J=7.1 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=152.8, 146.8, 129.3, 125.9,
121.2, 119.9, 107.2, 32.2, 27.7, 26.9, 24.9, 22.9, 21.6, 14.4; IR
(film): n=2934, 2859, 1481, 1447, 1289, 1247, 828, 754 cmÀ1
;
dene-2,2-di-tert-butyl-4H-benzo[d]
[1,3,2]dioxasiline
2a;
HR-MS (FAB+): m/z=332.2170, calcd. for C20H32O2Si [M+
yield: 88 mg (0.25 mmol, 83%); Rf =0.4 (hexane); white
H]: 332.2172.
Adv. Synth. Catal. 2013, 355, 1585 – 1596
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1591

Euichul Lee et al.
FULL PAPERS
(Z)-2,2-Di-tert-butyl-4-(4-phenylbutylidene)-4H-benzo[d]-
1484, 1446, 1291, 1262, 938, 844, 830 cmÀ1; HR-MS (FAB+):
m/z=445.2571, calcd. for C26H38FO3Si [M+H]: 445.2574.
Data of the minor isomer collected from the 1:2.8 mix-
ture: Rf =0.3 (EtOAc:hexane=1:10); colorless oil. H NMR
(400 MHz, CDCl3): d=7.30–7.21 (m, 7H), 7.07–7.04ACHTUNGTRENNUNG(m,
ACHTUNGTRENNUNG
1
(hexane); colorless oil. H NMR (400 MHz, CDCl3): d=7.36
1
(dd, J=8.0, 1.7 Hz, 1H), 7.29–7.12 (m, 6H), 6.89–6.84 (m,
2H), 5.23 (t, J=7.2 Hz, 1H), 2.69 (t, J=7.8 Hz, 2H), 2.33
(q, J=7.4 Hz, 2H), 1.79 (quintet, J=7.8 Hz, 2H), 1.06 (s,
18H); 13C NMR (100 MHz, CDCl3): d=152.4, 146.9, 142.7,
129.1, 128.4, 128.2, 125.6, 123.5, 120.9, 119.6, 106.2, 35.8,
31.4, 27.2, 26.5, 24.6; IR (film): n=3026, 2934, 2859, 1474,
1455, 1232, 1116, 753, 658 cmÀ1; HR-MS (FAB+): m/z=
394.2324, calcd. for C25H34O2Si [M+H]: 394.2328.
1H), 6.87 (td, J=7.5, 1.0 Hz, 1H), 4.47 (d, J=4.3 Hz, 1H),
4.43–4.40 (m, 1H), 3.17 (s, 1H), 1.60–1.50 (m, 1H), 1.45–
1.25 (m, 3H), 1.14 (d, J=0.8 Hz, 9H), 1.02 (d, J=0.8 Hz,
9H), 0.89 (t, J=7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=204.2, 152.6, 134.3, 132.5, 130.2, 129.9, 129.6, 128.6, 127.5,
121.4, 120.3 (d, J=3.1 Hz), 71.5, 61.8, 36.7, 26.7 (d, J=
4.4 Hz), 20.5 (d, J=14.4 Hz), 20.3 (d, J=13.3 Hz), 19.1, 13.9;
19F NMR (376 MHz, CDCl3): d=À155.0; IR (film): n=3465,
2936, 2863, 1682, 1598, 1483, 1447, 1294, 1259, 938, 845,
(Z)-2,2-Di-tert-butyl-4-(4-chlorobutylidene)-4H-benzo-
[d]ACHTUNGTRENNUNG[1,3,2]dioxasiline (2h): yield: 88% (NMR); Rf =0.4
1
(hexane); colorless oil. H NMR (400 MHz, CDCl3): d=7.36
(dd, J=7.8, 1.6 Hz, 1H), 7.17–7.13 (m, 1H), 6.90–6.84 (m,
2H), 5.18 (t, J=7.3 Hz, 1H), 3.60 (t, J=6.6 Hz, 2H), 2.43
(q, J=7.3
831 cmÀ1
;
HR-MS (FAB+): m/z=445.2572, calcd. for
C26H38FO3Si [M+H]: 445.2574; found: .
1-(2-(Di-tert-butylfluorosilyloxy)phenyl)-3-hydroxy-2-(p-
tolyl)hexan-1-one (4b): yield: 89 mg (65% ), Data of the
major isomer collected from the 1:2.1 mixture: Rf =0.4
(EtOAc:hexane=1:10); colorless oil. 1H NMR (400 MHz,
CDCl3): d=7.33 (dd, J=7.8, 1.8 Hz, 1H), 7.23–7.19 (m,
1H), 7.06–7.01 (m, 5H), 6.86 (td, J=7.5, 1.0 Hz, 1H), 4.49
(d, J=9.1 Hz, 1H), 4.38–4.32 (m, 1H), 2.99 (dd, J=3.2,
1.3 Hz, 1H), 2.25 (s, 3H), 1.58–1.50 (m, 1H), 1.33–1.21 (m,
3H), 1.17 (d, J=0.9 Hz, 9H), 0.97 (d, J=0.9 Hz, 9H), 0.81
(t, J=7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=152.8,
137.0, 132.7, 132.3, 130.4, 129.7, 129.6, 128.7, 121.3, 120.1 (d,
J=3.5 Hz), 72.7, 63.8, 35.6, 26.7 (d, J=9.4 Hz), 21.0, 20.4 (d,
J=7.6 Hz), 20.3 (d, J=7.4 Hz), 18.8, 13.9; 19F NMR
(376 MHz, CDCl3): d=À155.0; IR (film): n=3434, 2936,
2861, 1682, 1482, 1447, 1289, 1262, 936, 845, 830 cmÀ1; HR-
MS (FAB+): m/z=459.2729, calcd. for C27H40FO3Si [M+H]:
459.2731.
Data of the minor isomer collected from the 1:2.1 mixture
: Rf =0.3 (EtOAc:hexane=1:10), colorless oil. 1H NMR
(400 MHz, CDCl3): d=7.29–7.22 (m, 2H), 7.16 (dt, J=8.1,
1.8 Hz, 2H), 7.07–7.03 (m, 3H), 6.88 (td, J=7.5, 1.0 Hz,
1H), 4.43 (d, J=4.3 Hz, 1H), 4.41–4.36 (m, 1H), 3.15–3.14
(m, 1H), 2.28 (s, 3H), 1.56–1.49 (m, 1H), 1.45–1.25 (m, 3H),
1.14 (d, J=0.9 Hz, 9H), 1.02 (d, J=0.9 Hz, 9H), 0.89 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=204.2, 152.6,
137.1, 132.4, 131.1, 129.7, 129.6, 129.3, 121.4, 120.2 (d, J=
3.4 Hz), 71.5, 61.4, 36.7, 26.7 (d, J=5.1 Hz), 21.0, 20.6 (d, J=
12.4 Hz), 20.3 (d, J=13.9 Hz), 19.1, 13.9; 19F NMR
(376 MHz, CDCl3): d=À155.0; IR (film): n=3477, 2936,
2862, 1681, 1484, 1446, 1289, 1263, 936, 845, 831 cmÀ1; HR-
MS (FAB+): m/z=459.2728, calcd. for C27H40FO3Si [M+H]:
459.2731; found: .
Hz, 2H), 1.93 (quintet, J=7.2 Hz, 2H), 1.06 (s, 18H);
13C NMR (100 MHz, CDCl3): d=152.5, 147.7, 129.4, 125.5,
120.9, 119.7, 104.2, 44.8, 32.7, 27.2, 26.5, 22.3, 21.2; IR (film):
n=2936, 1729, 1703, 1474, 1298, 1242, 906, 637 cmÀ1; HR-
MS (FAB+): m/z=353.1706, calcd. for C19H30ClO2Si [M+
H]: 353.1704.
Typical Experimental Procedures for Catalytic
Tandem Hydrosilyloxylation and Mukaiyama Aldol
Reaction in One-Pot
To a suspension of chloroACHTUNTGRNEUNG[tris(4-trifluoromethylphenyl)phos-
phine]gold(I) (10.5 mg, 5 mol%) and AgOTf (3.9 mg,
5 mol%) in DCE (0.6 mL) was added di-tert-butyl[2-(phe-
nylethynyl)phenoxy]silanol 1a (105.9 mg, 0.3 mmol) in DCE
(0.6 mL). After being stirred at 808C for 3 h at 808C, the re-
action mixture was cooled to room temperature and then,
CH2Cl2 (1.2 mL) was added. This solution at À788C was
added to the reaction mixture obtained from BF3·OEt2
(37.0 mL, 0.3 mmol) and butyraldehyde (54.1 mL, 0.6 mmol)
in CH2Cl2 (0.6 mL) at À788C via cannula. After the mixture
had ben stirred for 6 h at À788C, a phosphate buffer solu-
tion (pH 7, 1 mL) was added. The reaction mixture was
warmed to room temperature over 1 h. After being stirred
at 258C for 15 min, the reaction mixture was dried over
MgSO4, filtered and washed with CH2Cl2 (3ꢁ2 mL) and the
combined organic layers were concentrated under reduced
pressure. The crude product was purified by column chro-
matography (EtOAc:hexane=1:10) to give 1-{2-[(di-tert-bu-
tylfluorosilyl)oxy]-phenyl}-3-hydroxy-2-phenylhexan-1-one
4a as a colorless oil (dr=1:2.8); yield: 89 mg (0.20 mmol,
67%). Data of the major isomer collected from the 1:2.8
2-(4-Chlorophenyl)-1-(2-(di-tert-butylfluorosilyloxy)-
phenyl)-3-hydroxyhexan-1-one (4c): yield: 76 mg (53%).
Data for 1:1.1 mixture of distereoisomers: Rf =0.3 (EtOA-
1
mixture
: Rf =0.4 (EtOAc:hexane=1:10), colorless oil.
c:hexane=1:10); colorless oil. H NMR (400 MHz, CDCl3):
1H NMR (400 MHz, CDCl3): d=7.33 (dd, J=7.7, 1.8 Hz,
1H), 7.26–7.15 (m, 6H), 7.05–7.03 (m, 1H), 6.86 (td, J=
7.5 Hz, 1.0, 1H), 4.54 (d, J=9.1 Hz, 1H), 4.40–4.35 (m, 1H),
3.03 (d, J=3.5 Hz, 1H), 1.59–1.51 (m, 1H), 1.36–1.21 (m,
3H), 1.17 (d, J=0.8 Hz, 9H), 0.97 (d, J=0.8 hZ, 9H), 0.81
(t, J=7.1Hz, 3H); 13C NMR (100 MHz, CDCl3): d=203.4,
152.7, 135.8, 132.4, 130.35, 130.21, 129.7, 128.9, 127.4, 121.3,
120.2 (d, J=3.5 Hz), 72.8, 64.2, 35.7, 26.7, 26.6, 20.4 (d, J=
7.4 Hz), 20.3 (d, J=7.0 Hz), 18.8; 19F NMR (376 MHz,
CDCl3): d=À154.7; IR (film): n=3459, 2936, 2863, 1691,
d=7.34 (dd, J=7.7, 1.7 Hz, 1H), 7.28–7.19 (m, 9H), 7.12
(dt, J=9.0, 2.2 Hz, 2H), 7.08–7.05 (m, 2H), 6.92–6.88 (m,
2H), 4.52 (d, J=9.0 Hz, 1H), 4.52 (d, J=9.0 Hz, 1H), 4.46
(d, J=8.9 Hz, 1H), 4.42–4.37 (m, 1H), 4.36–4.30 (m, 1H),
3.20 (d, J=1.9 Hz, 1H), 2.94 (dd, J=4.3, 0.9 Hz, 1H), 1.56–
1.48 (m, 2H), 1.43–1.19 (m, 6H), 1.16 (d, J=0.9 Hz, 9H),
1.13 (d, J=0.9 Hz, 9H), 1.02 (d, J=0.9 Hz, 9H), 0.96 (d, J=
0.9 Hz, 9H), 0.89 (t, J=7.3 Hz, 3H), 0.82 (t, J=7.1 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=203.9, 202.9, 152.8, 152.6,
139.3 134.4, 133.5, 133.3, 132.8, 132.79, 132.74, 131.3, 130.1,
1592
asc.wiley-vch.de
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1585 – 1596

Tandem Gold-Catalyzed Hydrosilyloxylation–Aldol and –Mannich Reaction with Alkynylaryloxysilanols
130.0, 129.9, 129.67, 129.60, 129.2, 129.1, 128.7, 121.6, 121.4,
120.38 (d, J=3.0 Hz), 120.30 (d, J=3.0 Hz), 72.7, 71.2, 63.3,
60.9, 36.7, 35.7, 27.4, 26.7 (d, J=1.9 Hz), 26.6 (d, J=3.6 Hz),
20.5–20.3 (m, 2C), 19.1, 18.7, 13.9, 13.8; 19F NMR (376 MHz,
CDCl3): d=À154.9, À154.7; IR (film): n=3475, 2934, 2892,
1580, 1472, 1289, 1250, 928, 829, 752 cmÀ1; HR-MS (FAB+):
m/z=479.2182, calcd. for C26H37ClFO3Si [M+H]: 479.2185.
2-Butyl-1-[2-(di-tert-butylfluorosilyloxy)phenyl]-3-hydr-
oxyhexan-1-one (4f): yield; 83 mg (65%). Data of the major
isomer collected from the 1:1.3 mixture: Rf =0.5 (EtOA-
(t, J=7.5 Hz, 2H), 1.78–1.30 (m, 8H), 1.10 (d, J=0.9 Hz,
9H), 1.05 (d, J=0.9 Hz, 9H), 0.88 (t, J=7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=207.3, 153.1, 141.7, 132.9,
130.4, 129.6, 128.3, 128.2, 125.7, 121.5, 120.4 (d, J=3.4 Hz),
71.7, 54.6, 37.4, 36.0, 29.1, 28.7, 26.7, 20.5 (d, J=4.3 Hz),
20.4 (d, J=4.5 Hz), 19.2, 13.9; 19F NMR (376 MHz, CDCl3):
d=À154.59; IR (film): n=3433, 2935, 2860, 1668, 1596,
1482, 1446, 1286, 1261, 935, 844, 830 cmÀ1; HR-MS (FAB+):
m/z=487.3042, calcd. for C29H43FO3Si [M+H]: 487.3044.
2-(3-Chloropropyl)-1-[2-(di-tert-butylfluorosilyloxy)-
phenyl]-3-hydroxyhexan-1-one (4h): yield; 71 mg (53%).
Data of the major isomer collected from the 1:1.8 mixture:
Rf =0.3 (EtOAc:hexane=1:10); colorless oil. 1H NMR
(400 MHz, CDCl3): d=7.51 (dd, J=7.7, 1.8 Hz, 1H), 7.39–
7.34 (m, 1H), 7.17 (dt, J=8.3, 1.3 Hz, 1H), 7.03 (dt, J=7.5,
0.9 Hz, 1H), 3.91–3.84 (m, 1H), 3.47–3.41 (m, 3H), 2.82 (d,
J=7.3 Hz, 1H), 1.91–1.73 (m, 4H), 1.57–1.32 (m, 4H), 1.11
(d, J=1.0 Hz, 9H), 1.07 (d, J=1.0 Hz, 9H), 0.90 (t, J=
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=206.5, 153.1,
133.1, 130.2, 129.6, 121.6, 120.5 (d, J=3.5 Hz), 71.7, 54.2,
44.7, 44.2, 37.2, 29.9, 26.7, 20.5 (d, J=5.7 Hz), 20.4 (d, J=
5.7 Hz), 19.2, 13.9; 19F NMR (376 MHz, CDCl3): d=
À154.54; IR (film): n=3465, 2937, 2863, 1688, 1482, 1446,
1283, 1259, 935, 439 cmÀ1; HR-MS (FAB+): m/z=445.2343,
calcd. for C23H39ClFO3Si [M+H]: 445.2341.
1
c:hexane=1:10); colorless oil. H NMR (400 MHz, CDCl3):
d=7.50 (dd, J=7.7, 1.8 Hz, 1H), 7.37–7.32 (m, 1H), 7.18–
7.15 (m, 1H), 7.02 (td, J=7.5, 1.0 Hz, 1H), 3.91–3.85 (m,
1H), 3.36 (q, J=6.1 Hz, 1H), 3.00 (d, J=7.3 Hz, 1H), 1.72–
1.67 (m, 2H), 1.61–1.33 (m, 4H), 1.30–1.21 (m, 4H), 1.11 (d,
J=1.0 Hz, 9H), 1.07 (d, J=1.0 Hz, 9H), 0.90 (t, J=7.2 Hz,
3H), 0.82 (t, J=7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3):
d=207.6, 153.1, 132.9, 130.6 (d, J=1.0 Hz), 129.6, 121.4,
120.4 (d, J=3.4 Hz), 71.7, 54.9, 37.4, 29.3, 29.2, 26.7 (d, J=
2.6 Hz), 22.9, 20.5 (d, J=7.6 Hz), 20.4 (d, J=7.6 Hz), 19.2,
14.0, 13.8; 19F NMR (376 MHz, CDCl3): d=À154.6; IR
(film): n=3432, 3072, 1681, 1574, 1378, 1160, 1125, 685 cmÀ1
;
HR-MS (FAB+): m/z=425.2885, calcd. for C24H42FO3Si
[M+H]: 425.2887.
Data of the minor isomer collected from the 1:1.3 mix-
ture: Rf =0.3 (EtOAc:hexane=1:10); white solid; mp 71–
778C. 1H NMR (400 MHz, CDCl3): d=7.44 (dd, J=7.7,
1.8 Hz, 1H), 7.37–7.33 (m, 1H), 7.17–7.14 (m, 1H), 7.03 (td,
J=7.5, 1.0 Hz, 1H), 4.02–3.97 (m, 1H), 3.35–3.31 (m, 1H),
2.76 (d, J=2.8 Hz, 1H), 1.81–1.48 (m, 3H), 1.41–1.16 (m,
6H), 1.09 (d, J=0.9 Hz, 1H), 1.06 (d, J=1.0 Hz, 9H), 0.92
(t, J=7.2 Hz, 3H), 0.81 (t, J=7.1 Hz, 3H), 0.81 (t, J=
7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=207.7, 152.9,
132.7, 130.8, 129.4, 121.6, 120.3 (d, J=3.5 Hz), 71.2, 54.7,
36.7, 30.3, 26.6, 25.9, 23.0, 20.5 (d, J=6.6 Hz), 20.4 (d, J=
6.6 Hz), 19.5, 14.0, 13.8; 19F NMR (376 MHz, CDCl3): d=
À154.7; IR (film): n=3448, 3072, 1684, 1574, 1379, 1161,
1127, 717 cmÀ1; HR-MS (FAB+): m/z=425.2888, calcd. for
C24H42FO3Si [M+H]: 425.2887.
Data of the minor isomer collected from the 1:1.8 mix-
ture: Rf =0.2 (EtOAc:hexane=1:10); colorless oil. H NMR
1
(400 MHz, CDCl3, 258C, TMS): d=7.44 (dd, J=7.7, 1.8 Hz,
1H), 7.39–7.34 (m, 1H), 7.17–7.15 (m, 1H), 7.04 (td, J=7.5,
1.0 Hz, 1H), 4.04–4.00 (m, 1H), 3.50–3.42 (m, 2H), 3.41–
3.36 (m, 1H), 1.94–1.48 (m, 7H), 1.43–1.30 (m, 2H), 1.09 (d,
J=1.0 Hz, 9H), 1.06 (d, J=1.0 Hz, 9H), 0.92 (t, J=7.2 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=206.7, 152.9, 132.9,
130.4, 129.5, 121.8, 120.4 (d, J=2.9 Hz), 71.1, 54.2, 44.9, 36.8,
30.9, 26.7, 23.5, 20.5 (d, J=7.4 Hz), 20.3 (d, J=7.3 Hz), 19.4,
13.9; 19F NMR (376 MHz, CDCl3): d=À154.65; IR (film):
=3465, 2937, 2863, 1682, 1597, 1482, 1446, 1283, 1258, 932,
426 cmÀ1
;
HR-MS (FAB+): m/z=445.2342, calcd. for
C23H39ClFO3Si [M+H]: 445.2341.
1-[2-(Di-tert-butylfluorosilyloxy)phenyl]-3-hydroxy-2-(3-
phenylpropyl)hexan-1-one (4g): yield: 58 mg (40%). Data of
the major isomer collected from the 1:1.3 mixture: Rf =0.4
(EtOAc:hexane=1:10); colorless oil. 1H NMR (400 MHz,
CDCl3): d=7.40 (dd, J=7.7, 1.8 Hz, 1H), 7.37–7.33 (m,
1H), 7.24–7.20 (m, 2H), 7.16–7.11 (m, 2H), 7.06–6.99 (m,
3H), 4.01–3.98 (m, 1H), 3.38–3.34 (m, 1H), 2.70 (s, 1H),
2.56–2.52 (m, 2H), 1.88–1.77 (m, 1H), 1.75–1.63 (m, 2H),
1.61–1.47 (m, 3H), 1.40–1.28 (m, 2H), 1.08 (d, J=0.9 Hz,
9H), 1.04 (d, J=0.9 Hz, 9H), 0.90 (t, J=7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3): d=207.4, 152.9, 141.9, 132.7,
130.6, 129.5, 128.3, 128.2, 125.7, 121.7, 120.3 (d, J=3.4 Hz),
71.1, 54.6, 36.7, 36.2, 29.8, 26.6, 25.9, 20.5 (d, J=9.7 Hz),
20.3 (d, J=9.5 Hz), 19.4, 13.9; 19F NMR (376 MHz, CDCl3):
d=À154.72; IR (film): n=3432, 2936, 2862, 1671, 1597,
1482, 1283, 1259, 933, 843, 831 cmÀ1; HR-MS (FAB+): m/z=
487.3046, calcd. for C29H43FO3Si [M+H]: 487.3044.
Typical Experimental Procedures for Catalytic
Tandem Hydrosilyloxylation and Mannich Reaction
in One-Pot
To
a suspension of chloroACHTUNTGERNUNG[tris(4-trifluoromethylphenyl)-
phosphine]gold(I) (10.5 mg, 5 mol%) and AgOTf (3.9 mg,
5 mol%) in DCE (0.6 mL) was added di-tert-butyl[2-(phe-
nylethynyl)phenoxy]silanol 2a (105.9 mg, 0.3 mmol) in DCE
(0.6 mL). After being stirred at 808C for 3 h, the reaction
mixture was cooled to room temperature and then, CH2Cl2
(1.2 mL) was added. This solution at À788C was added to
the reaction mixture obtained from BF3·OEt2 (37.0 mL,
0.3 mmol) and (E)-N-benzylidene-4-methylbenzenesulfona-
mide (155.6 mg, 0.6 mmol) in CH2Cl2 (0.6 mL) at À788C via
cannula. After the mixture had been stirred for 6 h at
À788C, a phosphate buffer solution (pH 7, 1 mL) was
added. The reaction mixture was warmed to room tempera-
ture over 1 h. After being stirred at 258C for 15 min, the re-
action mixture was dried over MgSO4, filtered and washed
with CH2Cl2 (3ꢁ2 mL) and the combined organic layers
were concentrated under reduced pressure. The crude prod-
uct was purified by column chromatography (EtOAc:hex-
Data of the minor isomer collected from the 1:1.3 mixture
: Rf =0.3 (EtOAc:hexane=1:10); colorless oil. 1H NMR
(400 MHz, CDCl3): d=7.47 (dd, J=7.8, 1.8 Hz, 1H), 7.37–
7.33 (m, 1H), 7.25–7.21 (m, 2H), 7.17–7.13 (m, 2H), 7.08–
7.06 (m, 2H), 7.01 (td, J=7.5, 0.9 Hz, 1H), 3.90–3.84 (m,
1H), 3.38 (q, J=6.0 Hz, 1H), 2.95 (d, J=7.3 Hz, 1H), 2.53
Adv. Synth. Catal. 2013, 355, 1585 – 1596
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1593

Euichul Lee et al.
FULL PAPERS
ane=1:10) to give N-{3-[2-(di-tert-butylfluorosilyloxy)phen-
yl]-3-oxo-1,2-diphenylpropyl}-4-methylbenzenesulfonamide
6a (dr=1:2.4) as white solid; yield: 98 mg (0.16 mmol,
53%). Data of the major isomer collected from the 1:2.4
mixture: Rf =0.2 (EtOAc:hexane=1:10, two times); white
(376 MHz, CDCl3): d=À155.1; IR (film): n=3434, 3032,
1690, 1573, 1325, 1158, 701 cmÀ1; HR-MS (FAB+): m/z=
646.2825, calcd. for C37H45FNO4SSi [M+H]: 646.2823.
N-{2-[2-(Di-tert-butylfluorosilyloxy)benzoyl]-1-phenylhex-
yl}-4-methylbenzenesulfonamide (6f): yield: 97 mg (53%).
Data of the major isomer collected from the 1:2.8 mixture:
Rf =0.25 (EtOAc:hexane=1:10, two times); yellow oil.
1H NMR (400 MHz, CDCl3): d=7.52 (d, J=8.3 Hz, 2H),
7.23–7.18 (m, 1H), 7.07–7.01 (m, 8H), 6.78–6.72 (m, 2H),
6.62 (dd, J=7.8, 1.7 Hz, 1H), 4.72 (dd, J=9.0, 3.7 Hz, 1H),
3.53–3.49 (m, 1H), 2.30 (s, 3H), 1.68–1.60 (m, 2H), 1.39–
1.33 (m, 1H), 1.26–1.16 (m, 3H), 1.08 (d, J=0.9 Hz, 9H),
0.99 (d, J=0.8 Hz, 9H), 0.79 (t, J=7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): d=205.4, 152.9, 142.6, 140.1, 138.3,
132.8, 130.1, 129.1, 129.0, 128.2, 127.0, 126.9, 126.7, 121.1,
120.1 (d, J=3.5 Hz), 58.2, 55.6, 30.4, 29.3, 26.7 (d, J=
14.5 Hz), 22.6, 21.4, 20.7 (d, J=14.2 Hz), 20.2 (d, J=
14.0 Hz), 13.7; 19F NMR (376 MHz, CDCl3): d=À154.7; IR
1
solid; mp 140–1448C. H NMR (400 MHz, CDCl3): d=7.34
(d, J=8.3 Hz, 2H), 7.21–7.14 (m, 2H), 7.12–7.06 (m, 10H),
7.00–6.96 (m, 3H), 6.79 (td, J=7.6, 1.0 Hz, 1H), 6.42 (d, J=
8.1 Hz, 1H), 4.95–4.87 (m, 2H), 2.31 (s, 3H), 1.07 (d, J=
0.9 Hz, 9H), 0.98 (d, J=0.9 Hz, 9H); 13C NMR (100 MHz,
CDCl3): d=200.4, 153.3, 142.4, 139.2, 137.7, 135.2, 133.1,
130.1, 129.2, 129.1, 129.0, 128.7, 128.1, 127.5, 127.3, 127.2,
126.9, 121.3, 120.5 (d, J=3.5 Hz), 61.7 (d, J=3.4 Hz), 53.4,
26.7 (d, J=7.7 Hz), 21.4, 20.5 (d, J=13.8 Hz), 20.4 (d, J=
14.3 Hz); 19F NMR (376 MHz, CDCl3): d=À154.1; IR
(film): n=3263, 3031, 1695, 1326, 1158, 1130, 699 cmÀ1; HR-
MS (FAB+): m/z=632.2663, calcd. for C36H43FNO4SSi [M+
H]: 632.2666.
(film): n=3286, 3030, 1691, 1573, 1326, 1185, 1160, 701 cmÀ1
;
Data of the minor isomer collected from the 1:2.4 mix-
ture: Rf =0.1 (EtOAc:hexane=1:10, two times); white solid;
HR-MS (FAB+): m/z=612.2976, calcd. for C34H47FNO4SSi
[M+H]: 612.2979.
1
mp 180–1888C. H NMR (400 MHz, CDCl3): d=7.33 (d, J=
8.2 Hz, 2H), 7.23–7.06 (m, 13H), 6.92–6.86 (m, 2H), 6.75
(td, J=7.5, 0.8 Hz, 1H), 5.06 (dd, J=9.6, 5.0 Hz, 1H), 4.86
(s, 1H), 4.69 (d, J=9.6 Hz, 1H), 2.37 (s, 3H), 0.99 (d, J=
0.8 Hz, 9H), 0.77 (d, J=0.8 Hz, 9H); 13C NMR (100 MHz,
CDCl3): d=197.3, 153.0, 142.9, 139.2, 136.7, 133.8, 132.6,
129.4, 129.2, 129.1, 128.8, 128.2. 128.17, 128.15, 127.5, 127.3,
120.9, 120.2 (d, J=3.1 Hz), 63.4, 59.6, 26.5 (d, J=16.4 Hz),
21.5, 20.4 (d, J=13.9 Hz), 20.1 (d, J=14.1 Hz); 19F NMR
(376 MHz, CDCl3): d=À155.1; IR (film): n=3279, 3032,
1691, 1573, 1366, 1158, 700 cmÀ1; HR-MS (FAB+): m/z=
632.2669, calcd. for C36H43FNO4SSi [M+H]: 632.2666.
Data of the minor isomer collected from the 1:2.8 mix-
ture: Rf =0.16 (EtOAc:hexane=1:10); brown solid; mp
148–1568C. 1H NMR (400 MHz, CDCl3): d=7.47 (d, J=
8.2 Hz, 2H), 7.26 (t, J=7.3 Hz, 1H), 7.08–7.01 (m, 9H), 6.85
(t, J=7.5 Hz, 1H), 5.53 (s, 1H), 4.63 (t, J=7.4 Hz, 1H),
3.65–3.60 (m, 1H), 2.29 (s, 3H), 1.75–1.70 (m, 1H), 1.58–
1.55 (m, 1H), 1.22–1.10 (m, 4H), 1.06 (s, 9H), 1.02 (s, 9H),
0.73 (t, J=7.0 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=
202.7, 153.0, 142.9, 139.3, 137.1, 132.7, 129.7, 129.3, 129.2,
128.1, 127.4, 127.2, 121.3, 120.4 (d, J=3.3 Hz), 58.8, 55.6,
29.0, 28.1, 26.7 (d, J=12.3 Hz), 22.8, 21.4, 20.7 (d, J=
14.5 Hz), 20.2 (d, J=13.9 Hz), 13.7; 19F NMR (376 MHz,
CDCl3): d=À154.6; IR (film): n=3273, 3033, 1686, 1574,
1325, 1185, 1159, 701 cmÀ1; HR-MS (FAB+): m/z=612.2976,
calcd. for C34H47FNO4SSi [M+H]: 612.2979.
N-{3-[2-(Di-tert-butylfluorosilyloxy)phenyl]-3-oxo-1-
phenyl-2-(p-tolyl)propyl}-4-methylbenzenesulfonamide (6b):
yield: 101 mg 52%). Data of the major isomer collected
from the 1:2.8 mixture: Rf =0.14 (EtOAc:hexane=1:10);
white solid; mp 149–1548C. 1H NMR (400 MHz, CDCl3):
d=7.34 (d, J=8.3 Hz, 2H), 7.20–7.10 (m, 4H), 7.09–7.06 (m,
3H), 6.96 (d, J=0.8 Hz, 5H), 6.88 (d, J=8.0 Hz, 2H), 6.77
(td, J=7.6, 1.0 Hz, 1H), 6.48 (d, J=8.0 Hz, 1H), 4.91–4.84
(m, 2H), 2.30 (s, 3H), 2.21 (s, 3H), 1.06 (d, J=0.8 Hz, 9H),
0.97 (d, J=0.8 Hz, 9H); 13C NMR (100 MHz, CDCl3): d=
200.6, 153.3, 142.3, 139.5, 137.8, 137.2, 133.1, 132.1, 130.1,
129.4, 129.2, 128.9, 128.8, 128.1, 127.3, 127.1, 126.9, 121.3,
120.4 (d, J=3.5 Hz), 61.8, 61.2, 26.7 (d, J=8.1 Hz), 21.4,
20.5 (d, J=13.9 Hz), 20.4 (d, J=14.5 Hz); 19F NMR
(376 MHz, CDCl3): d=À154.1; IR (film): n=3262, 3030,
1692, 1579, 1328, 1158, 700 cmÀ1; HR-MS (FAB+): m/z=
668.2640, calcd. for C37H44FNaNO4SSi [M+Na]: 668.2642.
Data of the minor isomer collected from the 1:2.8 mix-
ture: Rf =0.09 (EtOAc:hexane=1:10); white solid; mp 100–
3-Hydroxy-1-(2-hydroxyphenyl)-2-phenylhexan-1-one (7)
To a solution of 1-[2-(di-tert-butylfluorosilyloxy)-phenyl]-
3-hydroxy-2-phenylhexan-1-one
(4a-major)
(44.4 mg,
0.1 mmol) in THF (0.4 mL) at 08C was added TBAF (1.0M
solution in THF, 0.1 mL). After being stirred at 08C for 1 h,
reaction mixture was warmed to 258C over 1 h and then,
phosphate buffer solution (pH 7, 1 mL) was added. After
being stirred at 258C for 15 min, the reaction mixture was
dried over MgSO4, filtered and washed with CH2Cl2 (3ꢁ
2 mL) and the combined organic layers were concentrated
under reduced pressure. The crude product was purified by
column chromatography (EtOAc:hexane=1:7) to give 3-hy-
droxy-1-(2-hydroxyphenyl)-2-phenyl-hexan-1-one 7 as aco-
lorless oil; yield:26.7 mg (0.094 mmol, 94%); Rf =0.3
(EtOAc:hexane=1:7); colorless oil. 1H NMR (400 MHz,
CDCl3): d=12.30 (s, 1H), 7.80 (dd, J=8.1, 1.6 Hz, 1H),
7.41–7.37 (m, 1H), 7.33–7.29 (m, 3H), 7.27–7.23 (m, 1H),
6.93 (dd, J=8.4, 1.0 Hz, 1H), 6.82–6.78 (m, 1H), 4.61 (d, J=
8.8 Hz, 1H), 4.41–4.34 (m, 1H), 2.68 (dd, J=4.7, 0.6 Hz,
1H), 1.60–1.53 (m, 1H), 1.43–1.24 (m, 3H), 0.84 (t, J=
7.1 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=206.2, 163.3,
136.6, 136.1, 130.6, 129.2, 128.5, 127.7, 119.3, 118.9, 118.6,
73.0, 60.2, 35.7, 18.7, 13.9; IR (film): n=3647, 3544, 2935,
2859, 1639, 1446, 835; HR-MS (EI): m/z=284.1414, calcd.
for C18H20O3: 284.1412.
1
1038C. H NMR (400 MHz, CDCl3): d=7.33 (d, J=8.2 Hz,
2H), 7.26–7.23 (m, 2H), 7.16–7.11 (m, 4H), 7.07 (d, J=
8.0 Hz, 2H), 7.00–6.95 (m, 4H), 6.90 (d, J=8.2 Hz, 1H),
6.85 (dd, J=7.8, 1.7 Hz, 1H), 6.74 (td, J=15.1, 0.9 Hz, 1H),
5.10 (q, J=4.8 Hz, 1H), 4.80 (d, J=4.6 Hz, 1H), 4.63 (d, J=
9.7 Hz, 1H), 2.37 (s, 3H), 2.27 (s, 3H), 0.98 (d, J=0.8 Hz,
9H), 0.77 (d, J=0.8 Hz, 9H); 13C NMR (100 MHz, CDCl3):
d=197.3, 153.0, 142.8, 139.3, 138.0, 136.8, 132.5, 130.5, 129.9,
129.5, 129.3, 129.1, 128.7, 128.2, 128.1, 127.5, 127.3, 120.9,
120.1 (d, J=3.3 Hz), 63.2, 59.4, 26.5 (d, J=19.4 Hz), 21.5,
21.1, 20.4 (d, J=13.9 Hz), 20.1 (d, J=14.0 Hz); 19F NMR
1594
asc.wiley-vch.de
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1585 – 1596

Tandem Gold-Catalyzed Hydrosilyloxylation–Aldol and –Mannich Reaction with Alkynylaryloxysilanols
N-[3-(2-Hydroxyphenyl)-3-oxo-1,2-diphenylpropyl]-4-
methylbenzenesulfonamide (8)
1998, 110, 1096; Angew. Chem. Int. Ed. 1998, 37, 1044;
c) S. E. Denmark, O. J.-C. Nicaise, in: Comprehensive
Asymmetric Catalysis, (Eds.: E. N. Jacobsen, A. Pfaltz,
H. Yamamoto), Springer, Heidelberg, 1999, pp 923–961.
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Peng, Y. Ding, Synthesis 2003, 205; c) P. H. Lee, S. Kim,
A. Park, B. C. Chary, S. Kim, Angew. Chem. 2010, 122,
6958; Angew. Chem. Int. Ed. 2010, 49, 6806; d) B. C.
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To a solution of N-{3-[2-]di-tert-butylfluorosilyloxy)phen-
yl]-3-oxo-1,2-diphenylpropyl}-4-methylbenzenesulfonamide
(6a-major) (63.2 mg, 0.1 mmol) in THF (0.4 mL) at À788C
was added TBAF (1.0M solution in THF, 0.1 mL). After
being stirred at À788C for 3 h, reaction mixture was
warmed to room temperature over 1 h and then, phosphate
buffer solution (pH 7, 1 mL) was added. After being stirred
at 258C for 15 min, the reaction mixture was dried over
MgSO4, filtered and washed with CH2Cl2 (3ꢁ2 mL) and the
combined organic layers were concentrated under reduced
pressure. The crude product was purified by column chro-
matogram-phy (EtOAc:hexane=1:5) to give N-[3-(2-hy-
droxyphenyl)-3-oxo-1,2-diphenylpropyl]-4-methylbenzene-
sulfonamide 8 as a white solid; yield: 38.2 mg (0.081 mmol,
81%); Rf =0.2 (EtOAc:hexane=1:5); mp 199–2048C.
1H NMR (400 MHz, CDCl3): d=11.96 (s, 1H), 7.55 (dd, J=
8.2, 1.4 Hz, 1H), 7.36–7.30 (m, 3H), 7.12 (s, 5H), 7.04 (s,
5H), 6.93 (d, 2H), 6.88 (dd, J=8.4, 0.9 Hz, 1H), 6.68–6.64
(m, 1H), 6.19 (d, J=8.8 Hz, 1H), 5.07–5.03 (m, 1H), 4.98
(d, J=7.2 Hz, 1H), 2.29 (s, 3H); 13C NMR (100 MHz,
CDCl3): d=204.2, 163.2, 142.7, 138.7, 137.3, 136.8, 135.1,
130.2, 129.1, 128.9, 128.7, 128.2, 127.8, 127.3, 127.0, 126.8,
119.0, 118.9, 118.7, 61.2, 58.5, 21.4; IR (film): n=3262, 2936,
2861, 1696, 1446, 1288, 1158, 940, 425; HR-MS (EI): m/z=
471.1506, calcd. for C28H25NO4S: 471.1504.
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Acknowledgements
We thank the NCRL (2012-0001245) funded by the National
Research Foundation of Korea. We thank Dr. Sung Hong
Kim at the KBSI (Daegu) for obtaining the HR-MS data.
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ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2013, 355, 1585 – 1596