Rhodium-catalyzed arylation of acylsilanes with sodium tetraarylborates

Article abstract of DOI:10.1016/j.jorganchem.2014.05.005

Rhodium(I)-catalyzed arylation of benzoylsilanes with sodium tetraarylborates affords α-silyl benzhydrols, benzhydryl silyl ethers, benzhydrols, and diaryl ketones selectively depending on the catalyst, solvent, and temperature.

Full text of DOI:10.1016/j.jorganchem.2014.05.005

Accepted Manuscript
Rhodium-catalyzed arylation of acylsilanes with sodium tetraarylborates
Takanori Matsuda , Kohei Mizuno , Shoichi Watanuki
PII:
S0022-328X(14)00224-1
10.1016/j.jorganchem.2014.05.005
JOM 18577
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 25 February 2014
Revised Date: 1 May 2014
Accepted Date: 3 May 2014
Please cite this article as: T. Matsuda, K. Mizuno, S. Watanuki, Rhodium-catalyzed arylation of
acylsilanes with sodium tetraarylborates, Journal of Organometallic Chemistry (2014), doi: 10.1016/
j.jorganchem.2014.05.005.
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Rhodium-catalyzed arylation of acylsilanes with sodium tetraarylborates
Takanori Matsuda*, Kohei Mizuno, Shoichi Watanuki
Department of Applied Chemistry, Tokyo University of Science, 1–3 Kagurazaka, Shinjuku-ku,
Tokyo 162-8601, Japan
Abstract: Rhodium(I)-catalyzed arylation of benzoylsilanes with sodium tetraarylborates
affords α-silyl benzhydrols, benzhydryl silyl ethers, benzhydrols, and diaryl ketones
selectively depending on the catalyst, solvent, and temperature.
Keywords: Acylsilane, Addition, Alcohol, Boron, Homogeneous catalysis, Ketone, Rhodium
1. Introduction
Extensive studies have been conducted on rhodium(I)-catalyzed 1,2-addition reactions
of arylboron compounds to carbonyl compounds, which has become an indispensable
synthetic tool in the preparation of alcohols and ketones [1]. Several classes of carbonyl
* Corresponding author. Fax: +81 3 52614631.
E-mail address: mtd@rs.tus.ac.jp (T. Matsuda).
1

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compounds, including aldehydes [2], ketones [3], esters [4] and acid anhydrides [5], have
been identified as viable reaction partners for the rhodium(I)-catalyzed arylation with
arylboron compounds. However, to the best of our knowledge, the literature contains no
reports of the rhodium(I)-catalyzed arylation of acylsilanes with arylboron compounds [6,7].
We herein report that rhodium-catalyzed addition reactions of sodium tetraarylborates to
acylsilanes yield distinct arylation products depending on the reaction conditions employed.
2. Results and discussion
We began our investigation with the rhodium-catalyzed arylation of
benzoyltrimethylsilane (1a). When benzoylsilane 1a was reacted with sodium
tetraphenylborate (2a) in toluene at 90 °C in the presence of a catalytic amount of
[Rh(OH)(cod)]2 (cod = cycloocta-1,5-diene), 1,2-addition of arylrhodium(I) species to the
carbonyl group of 1a occurred to give diphenyl(trimethylsilyl)methanol (3aa) in 68% yield
(Table 1, entry 1) [8–10]. The carbonyl arylation is considered to proceed via 1,2-addition of
an arylrhodium(I) species to an acylsilane C=O bond. Other tetraarylborates 2b–e also
participated in the reaction with 1a to produce the corresponding α-silyl benzhydrols 3ab–ae
(entries 2–5). Product 3af derived from electron-rich tetraarylborate 2af (Ar = 4-MeOC6H4)
was unstable, and it rearranged to diaryl ketone 6f during isolation (entry 6) [11]. The half-life
for the rearrangement of relatively stable 3ad (Ar = 4-CF3C6H4) was determined by 1H NMR
to be approximately two weeks at room temperature in the absence of light [12].
Benzoylsilanes bearing SiMe2Ph and SiMe2t-Bu groups were also converted to the
corresponding α-silyl benzhydrols (3ba and 3ca), albeit with reduced efficacy (entries 7 and
2

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8). In cases where [RhCl(cod)]2 was used as a catalyst instead of [Rh(OH)(cod)]2, a decrease
in yields was observed (3aa: 52%, 3ba: 44%, 3ca: 42%).
Table 1
Rhodium-catalyzed arylation of benzoyltrimethylsilane to afford α-silyl benzhydrols 3.a
Entry
1 (Si)
2 (Ar)
Product Yield (%)
1
2
3
4
5
6
7
1a (SiMe3)
2a (Ph)
68b (65)c
3aa
2b (4-MeC6H4)
2c (3-MeC6H4)
2d (4-CF3C6H4)
2e (4-ClC6H4)
2f (4-MeOC6H4)
2a
56
46
60
52
1a
3ab
3ac
3ad
3ae
3af
1a
1a
1a
d
–
1a
1b (SiMe2Ph)
1c (SiMe2t-Bu)
53e
52f
3ba
3ca
8
2a
a
Conditions: 1 (0.10 mmol), 2 (0.15 mmol), and [Rh(OH)(cod)]2 (3.0 µmol, 6 mol% Rh) in
toluene (1.0 mL) at 90 °C for 8 h.
b 52% yield with [RhCl(cod)]2.
c Performed on a 0.5 mmol scale.
d Diaryl ketone 6f was isolated in 46% yield.
e 44% yield with [RhCl(cod)]2.
f 42% yield with [RhCl(cod)]2.
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In addition to the benzoylsilanes 1a–c, acetyl(trimethylsilyl)silane (1d) was also
utilized as the substrate for the rhodium-catalyzed arylation with 2 (Scheme 1). The reaction
of 1d and 2a furnished 1-phenyl-1-silylethanol 3da in 60% yield.
Scheme 1. Arylation of acetylsilane 1d with 2a
In contrast, the reaction performed in 1,4-dioxane in the presence of [RhCl(cod)]2
provided benzhydryl trimethylsilyl ether (4aa) in 81% NMR yield (Scheme 2). The silyl ether
4aa was desilylated during chromatography over silica gel to afford benzhydrol (5a) in 59%
yield. The formation of 4aa can be accounted for by considering the Brook-type 1,4-
rhodium/silicon
exchange
occurring
with
the
intermediate
[diphenyl(trimethylsilyl)methoxy]rhodium(I) [13,14,15]. Similar results were obtained when
the reaction was performed in the absence of light (4aa, 53% NMR yield), indicating that
siloxycarbene generated by a photoinduced 1,2-silyl shift might not be involved in the
process.
Scheme 2. Rhodium-catalyzed arylation of 1a affording benzhydryl silyl ether 4
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The reaction performed in protic solvents led to the exclusive formation of desilylated
benzhydrols 5 (Table 2). The arylation of 1a with 2a in EtOH in the presence of [RhCl(cod)]2
produced alcohol 5a in 73% yield. Because 3aa was recovered unchanged when heated at 90
°C in EtOH both in the presence and absence of the rhodium catalyst, the formation of 5a may
be ascribed to the desilylation of 4aa instead of 3aa under these catalytic conditions.
Phenyl(tolyl)methanols (5b and 5c) were obtained from the reaction of 1a with tolylborates
(2b and 2c) (entries 2 and 3). Although borates 2d and 2e failed to give benzhydrols 5, 4-
methoxyphenyl derivative 2f was successfully arylated with 1a to afford 5f in 61% yield
(entry 4). The use of dimethyl(phenyl)silyl derivative 1b for the reaction with 2a also led to
the formation of desired product 5a in 83% yield (entry 5), whereas the reaction of 1c
provided TBS ether 4ca, which was resistant to desilylation under the investigated reaction
conditions (entry 6).
Table 2
Rhodium-catalyzed arylation of 1 to afford benzhydrols 5.a
Entry
1 (Si)
2 (Ar)
Product
5a
Yield (%)
1
2
3
4
5
1a (SiMe3)
2a (Ph)
73 (84)b
87
2b (4-MeC6H4)
2c (3-MeC6H4)
2f (4-MeOC6H4)
2a
1a
5b
42
1a
5c
61
1a
5f
1b (SiMe2Ph)
83
5a
5

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6
1c (SiMe2t-Bu)
2ac
4cad
50e
a
Conditions: 1 (0.10 mmol), 2 (0.15 mmol), and [RhCl(cod)]2 (3.0 µmol, 6 mol% Rh) in
EtOH (1.0 mL) at 90 °C for 16 h.
b Performed on a 0.5 mmol scale (14 h).
c 1.5 equiv of 2a was used.
d Benzhydryl tert-butyldimethylsilyl ether.
e 69% yield with 3 equiv of 2a.
The rhodium-catalyzed arylation of 1 under more forcing conditions gave rise to diaryl
ketones 6 (Table 3) [16,17]. Because the oxidation of alcohols 5 to ketone 6 under the
investigated reaction conditions was virtually unnoticeable, 6 appears to be formed directly
from α-silyl benzhydrols 3. Indeed, heating 3aa at 130 °C in p-xylene for 24 h, irrespective of
the presence of the rhodium catalyst, resulted in the formation of 6a (49% yield without Rh;
28% yield with Rh), in contrast to the inertness of 3 in solution at temperatures less than 90
°C (vide supra).
Table 3
Rhodium-catalyzed arylation of 1 to afford diaryl ketones 6.a
Entry
1 (Si)
1a (SiMe3)
1a
2 (Ar)
Product
6a
Yield (%)
67 (73)b
47
1
2
3
2a (Ph)
2b (4-MeC6H4)
2c (3-MeC6H4)
6b
55c
1a
6c
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4
5
6
7
2d (4-CF3C6H4)
2e (4-ClC6H4)
2f (4-MeOC6H4)
2ad
53
1a
6d
6e
6f
40
1a
39c
68
1a
1b (SiMe2Ph)
1c (SiMe2t-Bu)
6a
6a
8
2ad
36e
a
Conditions: 1 (0.10 mmol), 2 (0.15 mmol), and [RhCl(cod)]2 (3.0 µmol, 6 mol% Rh) in p-
xylene (1.0 mL) at 130 °C for 24 h.
b Performed on a 0.5 mmol scale (45 h).
c Determined by 1H NMR.
d 1.5 equiv of 2a was used.
e 46% yield with 3.0 equiv of 2a.
3. Conclusion
In summary, the addition of sodium tetraarylborates 2 to acylsilanes 1 occurred in the
presence of rhodium(I) catalysts. The reaction gave α-silyl benzhydrols 3, benzhydryl silyl
ethers 4, benzhydrols 5, and diaryl ketones 6 depending on the conditions employed (Scheme
3). Alcohols 5 and ketones 6 were derived only from silyl ethers 4 and silyl alcohols 3,
respectively.
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Scheme 3. Diagram for the rhodium-catalyzed arylation of acylsilanes
4. Experimental section
4.1 General Procedure for the rhodium-catalyzed arylation of acylsilanes with sodium
tetraarylborates
A Schlenk tube was charged with sodium tetraarylborate 2 (0.150 mmol) and
[Rh(OH)(cod)]2 (3 µmol, 6 mol% Rh). The tube was evacuated and backfilled with nitrogen,
and then acylsilane 1 (0.100 mmol) and toluene (1.0 mL) were added via syringe through the
septum. After being heated at 90 °C for 8 h, the reaction mixture was filtered through a plug
of Florisil® washing with hexane–AcOEt (5:1), and the filtrate was concentrated. Purification
by preparative TLC on silica gel (hexane–AcOEt) afforded α-silyl benzhydrol 3.
4.1.1. Diphenyl(trimethylsilyl)methanol (3aa).
Pale yellow oil. IR (ν/cm–1): 2962, 1250, 837, 760, 702; 1H NMR (300 MHz, CDCl3) δ
0.13 (s, 9H), 1.97 (s, 1H), 7.17–7.24 (m, 2H), 7.27–7.38 (m, 8H); 13C NMR (75.5 MHz,
CDCl3) δ –2.3, 75.7, 126.2, 126.6, 128.0, 146.6; HRMS (ESI) calcd for C16H20NaOSi [M +
Na]+ 279.1176, found 279.1179.
4.1.2. Phenyl(p-tolyl)(trimethylsilyl)methanol (3ab).
1
Pale yellow oil. IR (ν/cm–1): 3487, 2962, 1651, 1281, 1250, 841, 702; H NMR (300
MHz, CDCl3) δ 0.13 (s, 9H), 1.93 (s, 1H), 2.33 (s, 3H), 7.12 (d, J = 8.4 Hz, 2H), 7.15–7.36
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13
(m, 7H); C NMR (75.5 MHz, CDCl3) δ –2.3, 75.5, 126.0, 126.4, 126.7, 127.9, 128.8, 135.8,
143.8, 146.8; HRMS (ESI) calcd for C17H22NaOSi [M + Na]+ 293.1332, found 293.1327.
4.1.3. Phenyl(m-tolyl)(trimethylsilyl)methanol (3ac).
Pale yellow oil. IR (ν/cm–1): 2962, 1250, 841, 748, 702; 1H NMR (300 MHz, CDCl3) δ
0.13 (s, 9H), 1.96 (s, 1H), 2.33 (s, 3H), 7.02 (d, J = 7.5 Hz, 1H), 7.15–7.24 (m, 4H), 7.27–
7.37 (m, 4H); 13C NMR (75.5 MHz, CDCl3) δ –2.3, 21.7, 75.6, 123.8, 126.1, 126.5, 127.0,
127.2, 127.8, 128.0, 137.7, 146.6, 146.7; HRMS (ESI) calcd for C17H22NaOSi [M + Na]+
293.1332, found 293.1331.
4.1.4. Phenyl[4-(trifluoromethyl)phenyl](trimethylsilyl)methanol (3ad).
1
Pale yellow oil. IR (ν/cm–1): 3479, 2962, 1250, 1103, 887, 841, 756, 702; H NMR
13
(300 MHz, CDCl3) δ 0.05 (s, 9H), 1.93 (s, 1H), 7.15–7.38 (m, 7H), 7.42–7.52 (m, 2H); C
NMR (75.5 MHz, CDCl3) δ –2.4, 75.7, 124.3 (q, 1JC–F = 271.5 Hz), 124.8 (q, 3JC–F = 3.7 Hz),
2
125.7, 126.4, 126.9, 128.0 (q, JC–F = 32.3 Hz), 128.4, 146.1, 150.5; HRMS (ESI) calcd for
C17H19F3NaOSi [M + Na]+ 347.1049, found 347.1055.
4.1.5. (4-Chlorophenyl)(phenyl)(trimethylsilyl)methanol (3ae).
1
Pale yellow oil. IR (ν/cm–1): 3479, 2962, 1250, 1211, 1095, 1003, 887, 841, 764; H
13
NMR (500 MHz, CDCl3) δ 0.12 (s, 9H), 1.96 (br s, 1H), 7.19–7.35 (m, 9H); C NMR (125.7
MHz, CDCl3) δ –2.4, 75.3, 126.6, 126.7, 127.8, 128.0, 128.2, 131.8, 145.1, 146.3; HRMS
(ESI) calcd for C16H19ClNaOSi [M + Na]+ 313.0786, found 313.0792.
4.1.6. [Dimethyl(phenyl)silyl]diphenylmethanol (3ba).
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1
Pale yellow oil. IR (ν/cm–1): 3556, 3062, 1250, 810, 741, 702; H NMR (300 MHz,
13
CDCl3) δ 0.39 (s, 6H), 2.08 (s, 1H), 7.15–7.41 (m, 15H); C NMR (75.5 MHz, CDCl3) δ –
3.9, 75.7, 126.2, 126.6, 127.6, 127.9, 129.3, 135.0, 136.4, 146.0; HRMS (ESI) calcd for
C21H22NaOSi [M + Na]+ 341.1332, found 341.1332.
4.1.7. (tert-Butyldimethylsilyl)diphenylmethanol (3ca).
1
Pale yellow oil. IR (ν/cm–1): 3444, 2958, 1246, 841, 760, 702; H NMR (300 MHz,
CDCl3) δ –0.01 (s, 9H), 1.46 (br s, 1H), 1.63 (s, 3H), 7.14–7.21 (m, 1H), 7.28–7.36 (m, 4H);
13C NMR (75.5 MHz, CDCl3) δ –4.3, 25.9, 69.8, 124.4, 125.3, 127.9, 148.1; HRMS (ESI)
calcd for C11H18NaOSi [M + Na]+ 217.1019, found 217.1020.
4.1.8. 1-Phenyl-1-(trimethylsilyl)ethanol (3da).
1
Pale yellow oil. IR (ν/cm–1): 3444, 2958, 1246, 841, 760, 702; H NMR (300 MHz,
CDCl3) δ –0.01 (s, 9H), 1.46 (br s, 1H), 1.63 (s, 3H), 7.14–7.21 (m, 1H), 7.28–7.36 (m, 4H);
13C NMR (75.5 MHz, CDCl3) δ –4.3, 25.9, 69.8, 124.4, 125.3, 127.9, 148.1; HRMS (ESI)
calcd for C11H18NaOSi [M + Na]+ 217.1019, found 217.1020.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.jorganchem.XXXX.XX.XXX.
References and Notes
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[12] At 0 °C, 3ad remained largely unchanged after one month.
[13] We thank one of the reviewers for suggesting this mechanism.
[14] Treatment of 3aa with KOH in 1,4-dioxane–H2O (100:1) at 80 °C resulted in a clean
conversion to 5a. However, 3aa remained unaltered when heated at 80 °C in 1,4-
dioxane, both in the presence and absence of the rhodium catalyst.
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ref 10a.
[16] For rhodium-catalyzed synthesis of ketones from aldehydes and potassium
aryltrifluoroborates under hydrogen transfer conditions, see O. Chuzel, A. Roesch, J.-
P. Genet, S. Darses, J. Org. Chem. 73 (2008) 7800–7802. See also ref 2g.
14

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[17] For palladium-catalyzed cross-coupling of acylsilanes and aryl bromides giving diaryl
ketones, see J.R. Schmink, S.W. Krska, J. Am. Chem. Soc. 133 (2011) 19574–19577.
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• Addition of sodium tetraarylborates to acylsilanes occurs in the presence of
rhodium(I) catalysts.
• Four different arylated products are obtained depending on the reaction conditions
employed.
• α-Silyl benzhydrols are converted into the corresponding dirayl ketones.

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Supporting Information
Rhodium-catalyzed arylation of acylsilanes with sodium tetraarylborates
Takanori Matsuda *, Kohei Mizuno, Shoichi Watanuki
Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku,
Tokyo 162-8601, Japan
E-mail: mtd@rs.tus.ac.jp
General. All reactions were carried out with standard Schlenk techniques. Column
chromatography was carried out on Wakogel C-200 (75–150 µm). Preparative thin-layer
chromatography was performed on Wakogel® B-5F. Proton chemical shifts were referenced to
residual CHCl3 signal at 7.26 ppm. Carbon chemical shifts were referenced to CDCl3 at 77.0 ppm.
Materials. Acylsilanes (1b and 1c) [1] and sodium tetraarylborates (2b–f) [2] were prepared
by the literature methods. All other commercially available chemical resources were used as
received without further purification.
[1]
[2]
J.R. Huckins, S.D. Rychnovsky, J. Org. Chem. 68 (2003) 10135–10145.
(a) T. Alaviuhkola, J. Bobacka, M. Nissinen, K. Rissanen, A. Ivaska, J. Pursiainen, Chem. Eur. J. 11 (2005)
2071–2080;
(b) R. Shintani, Y. Tsutsumi, M. Nagaosa, T. Nishimura, T. Hayashi, J. Am. Chem. Soc. 131 (2009) 13588–
13589.
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General Procedure: Rhodium-Catalyzed Arylation of Acylsilanes 1 with Sodium
Tetraarylborates 2
Diphenyl(trimethylsilyl)methanol (3aa). Table 1, Entry 1: A Schlenk tube was charged
with NaBPh4 (2a, 51.5 mg, 0.150 mmol) and [Rh(OH)(cod)]2 (1.4 mg, 3.1 µmol, 6 mol% Rh). The
tube was evacuated and backfilled with nitrogen, and then benzoyltrimethylsilane (1a, 17.9 mg,
0.100 mmol) and toluene (1.0 mL) were added via syringe through the septum. The mixture was
heated at 90 °C for 8 h. The reaction mixture was filtered through a plug of Florisil® washing with
hexane–AcOEt (5:1), and the filtrate was concentrated. Purification by preparative TLC on silica
gel (hexane:AcOEt = 8:1) afforded the title compound (3aa, 17.6 mg, 0.069 mmol, 68%) as a pale
yellow oil. IR (ν/cm–1): 2962, 1250, 837, 760, 702; 1H NMR (300 MHz, CDCl3) δ 0.13 (s, 9H), 1.97
13
(s, 1H), 7.17–7.24 (m, 2H), 7.27–7.38 (m, 8H); C NMR (75.5 MHz, CDCl3) δ –2.3, 75.7, 126.2,
126.6, 128.0, 146.6; HRMS (ESI) calcd for C16H20NaOSi [M + Na]+ 279.1176, found 279.1179.
Phenyl(p-tolyl)(trimethylsilyl)methanol (3ab). Table 1, Entry 2: According to the General
Procedure, 1a (17.1 mg, 0.096 mmol), 2b (60.0 mg, 0.151 mmol), and [Rh(OH)(cod)]2 (1.5 mg, 3.3
µmol, 7 mol% Rh) were reacted in toluene (1.0 mL) at 90 °C for 6.5 h. Purification by preparative
TLC on silica gel (hexane:AcOEt = 15:1) afforded the title compound (14.6 mg, 0.054 mmol, 56%)
1
as a pale yellow oil. IR (ν/cm–1): 3487, 2962, 1651, 1281, 1250, 841, 702; H NMR (300 MHz,
13
CDCl3) δ 0.13 (s, 9H), 1.93 (s, 1H), 2.33 (s, 3H), 7.12 (d, J = 8.4 Hz, 2H), 7.15–7.36 (m, 7H); C
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NMR (75.5 MHz, CDCl3) δ –2.3, 75.5, 126.0, 126.4, 126.7, 127.9, 128.8, 135.8, 143.8, 146.8;
HRMS (ESI) calcd for C17H22NaOSi [M + Na]+ 293.1332, found 293.1327.
Phenyl(m-tolyl)(trimethylsilyl)methanol (3ac). Table 1, Entry 3: According to the General
Procedure, 1a (17.3 mg, 0.097 mmol), 2c (59.6 mg, 0.150 mmol), and [Rh(OH)(cod)]2 (1.5 mg, 3.3
µmol, 7 mol% Rh) were reacted in toluene (1.0 mL) at 90 °C for 2.5 h. Purification by preparative
TLC on silica gel (hexane:AcOEt = 20:1) afforded the title compound (12.2 mg, 0.045 mmol, 46%)
as a pale yellow oil. IR (ν/cm–1): 2962, 1250, 841, 748, 702; 1H NMR (300 MHz, CDCl3) δ 0.13 (s,
9H), 1.96 (s, 1H), 2.33 (s, 3H), 7.02 (d, J = 7.5 Hz, 1H), 7.15–7.24 (m, 4H), 7.27–7.37 (m, 4H); 13C
NMR (75.5 MHz, CDCl3) δ –2.3, 21.7, 75.6, 123.8, 126.1, 126.5, 127.0, 127.2, 127.8, 128.0, 137.7,
146.6, 146.7; HRMS (ESI) calcd for C17H22NaOSi [M + Na]+ 293.1332, found 293.1331.
Phenyl[4-(trifluoromethyl)phenyl](trimethylsilyl)methanol (3ad). Table 1, Entry 4:
According to the General Procedure, 1a (16.1 mg, 0.090 mmol), 2d (92.1 mg, 0.150 mmol), and
[Rh(OH)(cod)]2 (1.4 mg, 3.1 µmol, 7 mol% Rh) were reacted in toluene (1.0 mL) at 100 °C for 2.5
h. Purification by preparative TLC on silica gel (hexane:AcOEt = 20:1) afforded the title compound
(17.5 mg, 0.054 mmol, 60%) as a pale yellow oil. IR (ν/cm–1): 3479, 2962, 1250, 1103, 887, 841,
1
756, 702; H NMR (300 MHz, CDCl3) δ 0.05 (s, 9H), 1.93 (s, 1H), 7.15–7.38 (m, 7H), 7.42–7.52
13
1
3
(m, 2H); C NMR (75.5 MHz, CDCl3) δ –2.4, 75.7, 124.3 (q, JC–F = 271.5 Hz), 124.8 (q, JC–F
=
3.7 Hz), 125.7, 126.4, 126.9, 128.0 (q, 2JC–F = 32.3 Hz), 128.4, 146.1, 150.5; HRMS (ESI) calcd for
C17H19F3NaOSi [M + Na]+ 347.1049, found 347.1055.
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(4-Chlorophenyl)(phenyl)(trimethylsilyl)methanol (3ae). Table 1, Entry 5: According to
the General Procedure, 1a (17.9 mg, 0.100 mmol), 2e (72.0 mg, 0.150 mmol), and [Rh(OH)(cod)]2
(1.4 mg, 3.1 µmol, 6 mol% Rh) were reacted in toluene (1.0 mL) at 90 °C for 2 h. Purification by
preparative TLC on silica gel (hexane:AcOEt = 20:1) afforded the title compound (15.1 mg, 0.052
mmol, 52%) as a pale yellow oil. IR (ν/cm–1): 3479, 2962, 1250, 1211, 1095, 1003, 887, 841, 764;
13
1H NMR (500 MHz, CDCl3) δ 0.12 (s, 9H), 1.96 (br s, 1H), 7.19–7.35 (m, 9H); C NMR (125.7
MHz, CDCl3) δ –2.4, 75.3, 126.6, 126.7, 127.8, 128.0, 128.2, 131.8, 145.1, 146.3; HRMS (ESI)
calcd for C16H19ClNaOSi [M + Na]+ 313.0786, found 313.0792.
(4-Methoxyphenyl)(phenyl)methanone (6f). Table 1, Entry 6: According to the General
Procedure, 1a (17.8 mg, 0.100 mmol), 2f (69.3 mg, 0.150 mmol), and [Rh(OH)(cod)]2 (1.4 mg, 6.4
µmol, 6 mol% Rh) were reacted in toluene (1.0 mL) at 90 °C for 18 h. Purification by preparative
TLC on silica gel (hexane:AcOEt = 8:1) afforded the title compound (9.8 mg, 0.046 mmol, 46%) as
white solid. 1H and 13C NMR spectra were identical to those in the literature [3].
Table 3, Entry 6: 1a (17.0 mg, 0.095 mmol), 2f (46.7 mg, 0.101 mmol), and [RhCl(cod)]2
(1.6 mg, 3.2 µmol, 7 mol% Rh) were reacted in p-xylene (1.0 mL) at 130 °C for 42 h. Purification
by preparative TLC on silica gel (hexane:AcOEt = 15:1) afforded an inseparable mixture of 6f and
4,4′-dimethoxy-1,1′-biphenyl (10.7 mg, 75:25 by 1H NMR, 39%).
[3]
D. Xing, B. Guan, G. Cai, Z. Fang, L. Yang, Z. Shi, Org. Lett. 8 (2006) 693–696.
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[Dimethyl(phenyl)silyl]diphenylmethanol (3ba). Table 1, Entry 7: According to the
General Procedure, 1b (24.0 mg, 0.100 mmol), 2a (51.4 mg, 0.150 mmol), and [Rh(OH)(cod)]2 (1.4
mg, 3.1 µmol, 6 mol% Rh) were reacted in toluene (1.0 mL) at 90 °C for 6 h. Purification by
preparative TLC on silica gel (hexane:AcOEt = 15:1) afforded the title compound (16.9 mg, 0.053
1
mmol, 53%) as a pale yellow oil. IR (ν/cm–1): 3556, 3062, 1250, 810, 741, 702; H NMR (300
13
MHz, CDCl3) δ 0.39 (s, 6H), 2.08 (s, 1H), 7.15–7.41 (m, 15H); C NMR (75.5 MHz, CDCl3) δ –
3.9, 75.7, 126.2, 126.6, 127.6, 127.9, 129.3, 135.0, 136.4, 146.0; HRMS (ESI) calcd for
C21H22NaOSi [M + Na]+ 341.1332, found 341.1332.
(tert-Butyldimethylsilyl)diphenylmethanol (3ca). Table 1, Entry 8: According to the
General Procedure, 1c (22.0 mg, 0.100 mmol), 2a (51.4 mg, 0.150 mmol), and [Rh(OH)(cod)]2 (1.4
mg, 3.1 µmol, 6 mol% Rh) were reacted in toluene (1.0 mL) at 90 °C for 10 h. Purification by
preparative TLC on silica gel (hexane:AcOEt = 20:1) afforded the title compound (15.5 mg, 0.052
1
mmol, 52%) as a pale yellow oil. IR (ν/cm–1): 3518, 2931, 2854, 1257, 833, 764, 702; H NMR
(300 MHz, CDCl3) δ 0.17 (s, 6H), 0.77 (s, 9H), 2.01 (s, 1H), 7.15–7.23 (m, 2H), 7.26–7.35 (m, 4H),
7.44–7.52 (m, 4H); 13C NMR (75.5 MHz, CDCl3) δ –5.2, 18.8, 28.1, 76.9, 126.0, 126.1, 127.9,
146.8; HRMS (ESI) calcd for C19H26NaOSi [M + Na]+ 321.1645, found 321.1641.
1-Phenyl-1-(trimethylsilyl)ethanol (3da). Scheme 1: According to the General Procedure,
1d (11.8 mg, 0.102 mmol), 2a (51.4 mg, 0.150 mmol), and [Rh(OH)(cod)]2 (1.4 mg, 3.1 µmol, 6
mol% Rh) were reacted in toluene (1.0 mL) at 90 °C for 12 h. Purification by preparative TLC on
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silica gel (hexane:AcOEt = 10:1) afforded the title compound (11.8 mg, 0.061 mmol, 60%) as a
1
pale yellow oil. IR (ν/cm–1): 3444, 2958, 1246, 841, 760, 702; H NMR (300 MHz, CDCl3) δ –0.01
13
(s, 9H), 1.46 (br s, 1H), 1.63 (s, 3H), 7.14–7.21 (m, 1H), 7.28–7.36 (m, 4H); C NMR (75.5 MHz,
CDCl3) δ –4.3, 25.9, 69.8, 124.4, 125.3, 127.9, 148.1; HRMS (ESI) calcd for C11H18NaOSi [M +
Na]+ 217.1019, found 217.1020.
(Benzhydryloxy)trimethylsilane (4aa). Scheme 2: According to the General Procedure, 1a
(17.9 mg, 0.100 mmol), 2a (51.4 mg, 0.150 mmol), and [RhCl(cod)]2 (1.5 mg, 3.0 µmol, 6 mol%
Rh) were reacted in 1,4-dioxane (1.0 mL) at 80 °C for 2 h. Purification by preparative TLC on silica
gel (neutral, hexane:AcOEt = 10:1) afforded an inseparable mixture of 4aa and biphenyl (23.1 mg,
85:15 by 1H NMR, 81%). 1H and 13C NMR spectra were identical to those in the literature [4].
Diphenylmethanol (5a). Table 2, Entry 1: According to the General Procedure, 1a (24.8
mg, 0.139 mmol), 2a (52.3 mg, 0.153 mmol), and [RhCl(cod)]2 (2.2 mg, 4.5 µmol, 6 mol% Rh)
were reacted in EtOH (1.5 mL) at 90 °C for 13.5 h. Purification by preparative TLC on silica gel
(hexane:AcOEt = 8:1) afforded the title compound (18.6 mg, 0.101 mmol, 73%) as a white solid.
Mp. 65–66 °C. 1H and 13C NMR spectra were identical to those in the literature [5].
Table 2, Entry 5: 1b (24.0 mg, 0.10 mmol), 2a (35.9 mg, 0.105 mmol), and [RhCl(cod)]2
(1.5 mg, 3.0 µmol, 6 mol% Rh) were reacted in EtOH (1.0 mL) at 80 °C for 4 h. Purification by
[4]
[5]
G. Rajagopal, H. Lee, S.S. Kim, Tetrahedron 65 (2009) 4735–4741.
A.J. Ruddy, C.M. Kelly, S.M. Crawford, C.A. Wheaton, O.L. Sydora, B.L. Small, M. Stradiotto, L. Turculet,
Organometallics 32 (2013) 5581–5588.
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preparative TLC on silica gel (hexane:AcOEt = 15:1) afforded the title compound (15.3 mg, 0.083
mmol, 83%) as a white solid.
Phenyl(p-tolyl)methanol (5b). Table 2, Entry 2: According to the General Procedure, 1a
(16.4 mg, 0.092 mmol), 2b (39.7 mg, 0.100 mmol), and [RhCl(cod)]2 (1.4 mg, 2.8 µmol, 6 mol%
Rh) were reacted in EtOH (1.0 mL) at 80 °C for 5 h. Purification by preparative TLC on silica gel
(hexane:AcOEt = 10:1) afforded the title compound (15.8 mg, 0.080 mmol, 87%) as a white solid.
Mp. 53–54 °C. 1H and 13C NMR spectra were identical to those in the literature [6].
Phenyl(m-tolyl)methanol (5c). Table 2, Entry 3: According to the General Procedure, 1a
(17.5 mg, 0.098 mmol), 2c (39.8 mg, 0.100 mmol), and [RhCl(cod)]2 (1.5 mg, 3.0 µmol, 6 mol%
Rh) were reacted in EtOH (1.0 mL) at 90 °C for 4 h. Purification by preparative TLC on silica gel
(hexane:AcOEt = 8:1) afforded the title compound (8.1 mg, 0.041 mmol, 42%) as a white solid.
1
Mp. 52.5–53.0 °C. H NMR (CDCl3, 300 MHz) δ 2.34 (s, 3H), 5.82 (s, 1H), 7.06–7.11 (m, 1H),
13
7.14–7.42 (m, 8H); C NMR (CDCl3, 75.5 MHz) δ 21.5, 76.3, 123.6, 126.5, 127.2, 127.5, 128.3,
128.4, 128.5, 138.2, 143.7, 143.8; HRMS (ESI) calcd for C14H14NaO [M + Na]+ 221.0937, found
221.0938.
[6]
A.A. Oluyadi, S. Ma, S.; C.N. Muhoro, Organometallics 32 (2013) 70–78.
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(4-Methoxyphenyl)(phenyl)methanol (5f). Table 2, Entry 4: According to the General
Procedure, 1a (17.8 mg, 0.100 mmol), 2f (48.5 mg, 0.105 mmol), and [RhCl(cod)]2 (1.5 mg, 3.0
µmol, 6 mol% Rh) were reacted in EtOH (1.0 mL) at 80 °C for 12 h. Purification by preparative
TLC on silica gel (hexane:AcOEt = 10:1) afforded the title compound (13.1 mg, 0.061 mmol, 61%)
as a white solid. Mp 63–64 °C. 1H and 13C NMR spectra were identical to those in the literature [7].
(Benzhydryloxy)(tert-butyl)dimethylsilane (4ca). Table 2, Entry 6: According to the
General Procedure, 1c (22.0 mg, 0.100 mmol), 2a (51.4 mg, 0.150 mmol), and [RhCl(cod)]2 (1.5
mg, 3.0 µmol, 6 mol% Rh) were reacted in EtOH (1.0 mL) at 80 °C for 4 h. Purification by
preparative TLC on silica gel (hexane:AcOEt = 20:1) afforded the title compound (15.0 mg, 0.050
mmol, 50%) as a pale yellow oil. 1H NMR (300 MHz, CDCl3) δ –0.05 (s, 6H), 0.90 (s, 9H), 5.73 (s,
13
1H), 7.14–7.21 (m, 2H), 7.22–7.29 (m, 4H), 7.30–7.36 (m, 4H); C NMR (75.5 MHz, CDCl3) δ –
4.9, 18.3, 25.8, 76.6, 126.3, 126.9, 128.1, 145.2; HRMS (ESI) calcd for C19H26NaOSi [M + Na]+
321.1645, found 321.1644.
Benzophenone (6a). Table 3, Entry 1: According to the General Procedure, 1a (17.8 mg,
0.100 mmol), 2a (35.9 mg, 0.105 mmol), and [RhCl(cod)]2 (1.5 mg, 3.0 µmol, 6 mol% Rh) were
reacted in p-xylene (1.0 mL) at 130 °C for 24 h. Purification by preparative TLC on silica gel
[7]
M. Kuriyama, N. Ishiyama, R. Shimazawa, O. Onomura, Tetrahedron 66 (2010) 6814–6819.
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(hexane:AcOEt = 20:1) afforded the title compound (12.2 mg, 0.067 mmol, 67%) as a white solid.
Mp. 49.0–49.5 °C. 1H and 13C NMR spectra were identical to those in the literature [8].
Table 3, Entry 7: 1b (24.0 mg, 0.100 mmol), 2a (51.4 mg, 0.150 mmol), and [RhCl(cod)]2
(1.5 mg, 3.0 µmol, 6 mol% Rh) were reacted in p-xylene (1.0 mL) at 130 °C for 24 h. Purification
by preparative TLC on silica gel (hexane:AcOEt = 20:1) afforded the title compound (12.4 mg,
0.068 mmol, 68%) as a white solid.
Table 3, Entry 8: 1c (22.0 mg, 0.100 mmol), 2a (51.4 mg, 0.150 mmol), and [RhCl(cod)]2
(1.5 mg, 3.0 µmol, 6 mol% Rh) were reacted in p-xylene (1.0 mL) at 130 °C for 24 h. Purification
by preparative TLC on silica gel (hexane:AcOEt = 20:1) afforded the title compound (6.6 mg, 0.036
mmol, 36%) as a white solid.
Phenyl(p-tolyl)methanone (6b). Table 3, Entry 2: According to the General Procedure, 1a
(26.3 mg, 0.147 mmol), 2b (59.7 mg, 0.150 mmol), and [RhCl(cod)]2 (2.3 mg, 4.7 µmol, 6 mol%
Rh) were reacted in p-xylene (1.5 mL) at 130 °C for 42 h. Purification by preparative TLC on silica
gel (hexane:AcOEt = 15:1) afforded the title compound (13.7 mg, 0.070 mmol, 47%) as a white
solid. Mp. 56.5–57.0 °C. 1H and 13C NMR spectra were identical to those in the literature [9].
Phenyl(m-tolyl)methanone (6c). Table 3, Entry 3: According to the General Procedure, 1a
(17.8 mg, 0.100 mmol), 2c (40.0 mg, 0.100 mmol), and [RhCl(cod)]2 (1.5 mg, 3.0 µmol, 6 mol%
[8]
[9]
L. Meng, J. Su, Z. Zha, L. Zhang, Z. Zhang, Z. Wang, Chem. Eur. J. 19 (2013) 5542–5545.
W.-Y. Wu, T.-C. Lin, T. Takahashi, F.-Y. Tsai, C.-Y. Mou, ChemCatChem 5 (2013) 1011–1019.
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Rh) were reacted in p-xylene (1.0 mL) at 130 °C for 24 h. Purification by preparative TLC on silica
gel (hexane:AcOEt = 15:1) afforded an inseparable mixture of 6c and 3,3′-dimethyl-1,1′-biphenyl
1
(11.4 mg, 93:7 by 1H NMR, 55%). H and 13C NMR spectra were identical to those in the literature
[10].
Phenyl[4-(trifluoromethyl)phenyl]methanone (6d). Table 3, Entry 4: According to the
General Procedure, 1a (16.5 mg, 0.093 mmol), 2d (60.4 mg, 0.098 mmol), and [RhCl(cod)]2 (1.4
mg, 2.8 µmol, 6 mol% Rh) were reacted in p-xylene (1.0 mL) at 130 °C for 36 h. Purification by
preparative TLC on silica gel (hexane:AcOEt = 15:1) afforded the title compound (12.2 mg, 0.049
mmol, 53%) as a white solid. Mp. 72–73 °C. 1H and 13C NMR spectra were identical to those in the
literature [11].
(4-Chlorophenyl)(phenyl)methanone (6e). Table 3, Entry 5: According to the General
Procedure, 1a (17.3 mg, 0.097 mmol), 2e (48.0 mg, 0.100 mmol), and [RhCl(cod)]2 (1.5 mg, 3.0
µmol, 6 mol% Rh) were reacted in p-xylene (1.0 mL) at 130 °C for 30 h. Purification by preparative
TLC on silica gel (hexane:AcOEt = 8:1) afforded the title compound (8.4 mg, 0.039 mmol, 40%) as
1
13
a white solid. Mp. 114–115 °C. H and C NMR spectra were identical to those in the literature
[12].
[10] M. Li, M.; C. Wang, H. Ge, Org. Lett. 13 (2011) 2062–2064.
[11] A.T. Biju, F. Glorius, Angew. Chem., Int. Ed. 49 (2010) 9761–9764.
[12] L.J. Gooßen, F. Rudolphi, C. Oppel, N. Rodríguez, Angew. Chem., Int. Ed. 47 (2008) 3043–3045.
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3aa
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