Oxy effects on the platinum-catalyzed carbo- and oxacyclizations of 2-oxiranyl-1-(1-oxyalk-2-ynyl)benzenes

Article abstract of DOI:10.1002/adsc.201200187

We report new platinum-catalyzed protocols for the synthesis of carbocycles and oxacycles from 2-oxiranyl-1-(1-oxyalk-2-ynyl)benzenes. For 1,2,2-trisubstituted epoxides bearing an acyloxy group, their platinum-catalyzed cyclizations proceed through an ini

Full text of DOI:10.1002/adsc.201200187

FULL PAPERS
DOI: 10.1002/adsc.201200187
Oxy Effects on the Platinum-Catalyzed Carbo- and
Oxacyclizations of 2-Oxiranyl-1-(1-oxyalk-2-ynyl)benzenes
Rupsha Chaudhuri,a Samir Kundlik Pawar,a Kamalkishore Pati,a
and Rai-Shung Liua,*
a
Department of Chemistry, National Tsing-Hua University, Hsinchu, Taiwan, ROC
Fax : (+886)-3-571-1082; e-mail: rsliu@mx.nthu.edu.tw
Received: March 5, 2012; Revised: May 1, 2012; Published online: July 29, 2012
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201200187.
Abstract: We report new platinum-catalyzed proto- 2-naphthyl ketones through a selective 1,2-alkyl shift.
cols for the synthesis of carbocycles and oxacycles 1,1-Disubstituted epoxides bearing a siloxy group un-
from 2-oxiranyl-1-(1-oxyalk-2-ynyl)benzenes. For dergo an oxacyclization to give bicyclic ketals with
1,2,2-trisubstituted epoxides bearing an acyloxy high diastereoselectivity.
group, their platinum-catalyzed cyclizations proceed
through an initial 1,3-acyloxy shift, followed by an
intramolecular attack of an allenyl acetate at the car- Keywords: carbocyclization; catalysis; epoxides; oxa-
bonyl group, ultimately giving
cyclization; platinum
Introduction
3a over commonly used gold and platinum catalysts;
this initial epoxide was prepared as a diastereomeric
Gold- and platinum-catalyzed electrophilic activations mixture (1.8/1). Although gold complexes such as
of alkynes represent a recent advent in organic syn- PPh3AuCl/AgSbF6 and PPh3AuCl/AgOTf (5 mol%)
thesis.[1,2] Au- and Pt-catalyzed cyclizations of epoxy- enabled a complete consumption of starting 3a in di-
alkyne functionalities are powerful tools to access
complicated oxa- or carbocyclic products.[3,4] Previous-
ly, we reported the gold-catalyzed aromatization of 2-
oxiranyl-1-(methoxyalk-2-ynyl)benzenes 1 to form 2-
naphthyl aldehydes 2 through a novel 1,3-carbonyl
shift, as depicted in Scheme 1.[5] In the gold- and plati-
num-catalyzed cyclizations of propargylic alcohol de-
rivatives, the tethered oxy substituents influence the
chemoselectivity through their 1,n-shifts to the elec-
tron-deficient center.[6,7] Herein, we highlight such oxy
effects on acyloxy- and siloxy derivatives 3 and 5, pro-
viding 2-naphthyl ketones 4 and bicyclic ketals 6 effi-
ciently. Beside the oxy effects, epoxy structures are
crucial for the chemoselectivities. 2-Naphthyl alde-
hydes 2 and bicyclic ketals 6 are here produced more
efficiently from 1,1-disubtituted epoxides 1 and 5,
whereas 2-napthyl ketones 4 are preferably produced
with 1,2,2-trisubstituted epoxides 3.
Results and Discussion
As shown in Table 1, we examined the catalytic reac-
tions of 2-oxiranyl-1-(1-acetyloxyalk-2-ynyl)benzene Scheme 1. The oxy effect on chemoselectivity.
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Table 1. Screening of catalysts for compound 3a.
Entry
Catalyst
mol%
Time [min]
Temp. [oC]
Compound (yield)[b]
[c]
1
2
3
4
5
6
7
AuClPPh3/AgSbF6
AuClPPh3/AgOTf
AuCl3
AuCl3/CO
AuBr3
5
5
5
5
5
10
10
15
15
25
25
25
25
25
25
70
–
–
–
–
[c]
[c]
120
90
120
750
60
[c]
[c]
–
PtCl2/CO
PtCl2/CO
3a (90%)
4a (81%)
[a]
[3a]=0.135M, 1.8/1 mixture of two diastereomers.
Isolated yields are reported after silica column chromatography.
Complicated mixture of products.
[b]
[c]
chloroethane (DCE, 258C, 15 min), we isolated no tion on trans-1,2-disubstituted epoxide 3h that gave
pure compound. We turned to the less acidic AuCl3, desired ketone 4h in 69% yield, together with its re-
AuCl3/CO[8] and AuBr3 (entries 3–5), with which com- gioisomer 4h’ in 19% yield (entry 7). For the 1,1-dis-
pound 3a underwent slow decomposition to products ubstituted epoxide 3i, we obtained the desired ketone
in a complicated mixture. The use of PtCl2/CO[8] led 4i and 2-naphthyl aldehyde 1i in almost equal propor-
to the exclusive recovery of epoxide 3a (90%) in tions (47/49%), which were separable on a silica
DCE (258C) even after 12.5 h (entry 6). Hence, we column (entry 8). Herein, the use of PPh3AuCl/
operated the same reaction at 708C for 60 min to AgSbF6 in DCE (258C, 10 min) further increased the
allow an efficient transformation of species 3a into 2- yield of the desired 4i to 78%.[8] We prepared also ep-
naphthyl ketone 4a in 81% yield (entry 7). We per- oxides 3j–3n bearing a fluoro- or methoxy group at
formed a kinetic study to show the conversion of ep- the C-4 and C-5 phenyl carbons (entries 9–13); we ob-
oxide 3a versus time using AuCl3 and PtCl2 respec- tained the corresponding ketone products 4j, 4k and
tively (see the Supporting Information).
4m, 4n in satisfactory yields (>66%), whereas epox-
Table 2 shows the generalization of this 2-naphthyl ide 3l gave a messy mixture of products (entry 11).
ketone synthesis using acyloxy derivatives 3b–3n bear- Structural elucidations of ketones 4a, 4e, 4f and 1H-
1
ing varied alkynyl and oxiranyl substituents; these isochromene 7d relied on their H-NOE spectra.[9]
substrates are present as a mixture of two diastereo-
Starting epoxides 3 may undergo a platinum-cata-
mers. The reactions proceeded well with 1,2,2-trisub- lyzed epoxide-carbonyl rearrangement under our re-
stituted epoxides 3b–3g and 3j–3n to give only 2- action conditions (DCE, 708C). We tested this rear-
naphthyl ketones, whereas the other two epoxides 3h rangement with trisubstituted epoxides 7a and 7b;
and 3i were affected with side products 4h’ and 1i (en- indeed, the reaction is very facile and complete with
tries 7 and 8). We tested the reactions on internal 15 min at 288C. Herein, we were unable to obtain al-
alkyne substrates 3b and 3c (entries 1 and 2) that de- dehyde 7b’ in pure form due to its instability on
livered desired ketones 4b and 4c in 77 and 85% column chromatography (Scheme 2).
yields, respectively, whereas the same reaction on ter-
Scheme 3 shows a plausible mechanism to rational-
minal alkyne 3d provided 1H-isochromene 7d in 72% ize the observed 1,2-migration observed for 2-naph-
yield (entry 3). The cyclizations worked well with sub- thyl ketones 4e and 4f from trisubstituted epoxides 3e
strates 3e and 3f bearing varied oxiranyl substituents and 4f. Under our reaction conditions (DCE, 708C),
R=n-propyl and phenyl, giving the analogous ke- platinum catalyzes not only a 1,3-acyloxy shift,[6] but
tones 4e and 4f in 78 and 81% yields, respectively. also a epoxy-ketone rearrangement to form allenyl al-
Herein, we observed a 1,2-migration for the large R= dehyde A. An intramolecular cyclization[10] forms 1,2-
n-propyl and phenyl groups whereas the small methyl dihydronaphthalene B that reacts with residual water
moiety remained unmoved (entries 4 and 5). For tri- to give alcohol species C, in turn further giving allylic
substituted epoxide 3g bearing a cyclopentyl ring, we cation D. A final 1,2-shift in species D preferably pro-
obtained the corresponding ketone 4g (74% yield) ceeds with a methyl migration to attain a more stable
through a ring expansion. We tried this catalytic reac- cation E with R=n-Bu and Ph remaining unchanged
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Oxy Effects on the Platinum-Catalyzed Carbo- and Oxacyclizations
Table 2. Reaction scope of the carbocylization of acycloxy derivatives.
[a]
[Substrate]=0.135M, mixture of diastereomers.
Product yields are reported after separation from a silica column.
Complicated mixture of products.
[b]
[c]
according to a Wagner–Meerwein rearrangement.[11] generate H2O and Pt to furnish a second catalytic
The released Pt(OH)À reacts further with H+ to re- circle.
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tives.[5,11] As shown in Table 3, treatment of starting 5a
with PtCl2/CO (10 mol%) in DCE at 258C led to its
complete consumption to give bicyclic ketal 6a and
1H-isochromene 8a in 33% and 18% yields, respec-
tively (entry 1). At an elevated temperature (708C),
we obtained only 1H-isochromene 8a in 54% yield
(entry 2). We confirmed that oxacycle 8a was pro-
duced from ketal 6a in the presence of PtCl2/CO in
hot DCE (708C, 1.5 h); the yield was 86%. We at-
tempted to improve the chemoselectivity by using the
platinum catalyst at a decreased loading (7 mol%) in
Scheme 2. PtCl2-catalyzed epoxide-carbonyl rearrangement.
For curiosity, we prepared a siloxy derivative 5a to DCE (258C, 90 min). whereby, we obtained the de-
study its chemoselectivity toward the PtCl2/CO cata- sired ketal 6a in an increased yield (56%) with 1H-
lyst. Propargylic siloxy species cannot undergo a 1,3- isochromene 8a in 12% yield (entry 3). A brief reac-
shift like its acyloxy analogue, and is likewise unable tion period (20 min) further enhanced the yield of
to complex with platinum like its methoxy rela- ketal 6a to 86% (entry 4). The use of AuCl3/CO and
Scheme 3. A plausible mechanism for the formation of 2-naphthyl ketones.
Table 3. Platinum-catalyzed oxacyclization of siloxy species 5a.
Entry
Catalyst
mol%
Temp. [oC]
Time [min]
Product (yield [%][b])
1
2
3
4
5
6
PtCl2/CO
PtCl2/CO
PtCl2/CO
PtCl2/CO
AuCl3/CO
PPh3AuCl/AgSbF6
10
10
7
7
5
25
70
25
25
25
25
90
90
90
20
5
6a (33), 8a (18)
8a (54)
6a (56), 8a (12)
6a (86)
[c]
–
–
[c]
5
5
[a]
[5a]=0.135M, 1.4/1 mixture of two diastereomers.
Isolated yields are reported after chromatography.
Complicated mixture of products.
[b]
[c]
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Oxy Effects on the Platinum-Catalyzed Carbo- and Oxacyclizations
Table 4. Scope of the platinum-catalyzed oxacyclization cascade.
Entry
Substrate[a]
Time [min]
Products (Yields [%])[b]
1
2
R=n-Pr, R1 =Me (5b); dr=1.6/1
R=Me, R1 =n-Bu (5c); dr=2/1
20
20
6b (78)
6c (70)
3
4
5
R=Me, R1 =Me (5d); dr=1.9/1.6/1.2/1
R=Me, R1 =Et (5e); dr=1.8/1.8/1.4/1
R=n-Pr, R1 =Me (5f); dr=2/1.7/1.3/1
20
40
40
6d (71)
6e (66)
6f (69)
[c]
6
40
–
[c]
7
40
–
8
9
10
11
12
13
X=F, Y =H (5i); dr=1.2/1
X=H, Y=F (5j); dr=1.3/1
X=Cl, Y=H (5k); dr=1.4/1
X=H, Y=Cl (5l); dr=1.3/1
X=H, Y=OMe (5m); dr=1.4/1
X=Y=OMe (5n); dr=2/1
20
20
20
20
20
20
6i (72)
6j (70)
6k (70)
6l (74)
6m (70)
[c]
–
[a]
[epoxide]=0.135M, mixture of diastereomers.
Product yields are reported after separation from a silica column.
Complicated mixture of products.
[b]
[c]
PPh3AuCl/AgSbF6 led to a quick decomposition of 6i–6m in 70–74% yields. We obtained products in
starting 5a into a complicated mixture of products in a messy mixture from epoxide 5n bearing the metha-
DCE (258C, 5 min, entries 5 and 6).
nediyldioxy moiety at the phenyl C-4 and C-5 posi-
We prepared various epoxides 5b–5m to examine tions. Accordingly, this new ketal synthesis works
the scope of the platinum-catalyzed synthesis of bicy- more efficiently with 1,1-disubtituted epoxide sub-
clic ketals 6b–6m (Table 4).These reactions were ex- strates. Structural elucidations of ketones 6a, 6d and
1
tendable to 1,1-disubstituted epoxides 5b and 5c, 6f relied on their H-NOE spectra.[9]
giving desired bicyclic ketals 6b and 6c in 70–78%
As shown in Scheme 4, we prepared chiral propar-
yields. We tested the same reactions on 1,1,2-trisubsti- gylic alcohol (S)-9 with 74% ee, which further deliv-
tuted epoxides 5d–5f that also gave desired bicyclic ered starting epoxide 5a as a 2:1 diastereomeric mix-
ketals 6d–6f with 66–71% yields. For trans-1,2-disub- ture. Treatment of this epoxide 5a with PtCl2/CO in
stituted, and 1,2,2-trisubstituted epoxides 5g and 5h, DCE (258C, 25 min) gave bicyclic ketal 6a with 29%
their corresponding reactions gave products in a com- ee. In a separate experiment, we used chiral alcohol
plicated mixture (entry 6 and 7). Entries 8–13 show (S)-9 (76% ee) to prepare epoxide 5a with a 1:1 dia-
the results on 1,1-disubstituted epoxides 5i–5m bear- stereomeric mixture, upon silica separation; we ob-
ing a fluoro, chloro or methoxy substituent at their tained the resulting product 6a in only 3% ee.
phenyl C-4 and C-5 carbons, giving the desired ketals
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Scheme 4. Loss of chirality.
Scheme 5. A plausible mechanism for the formation of bicyclic ketal 6a.
The preceding results indicate that the ee values of ceed through an initial 1,3-acyloxy shift, followed by
ketal 6a depend on the diastereomeric ratios of the an intramolecular attack of an allenyl acetate at the
starting epoxide 5a. For starting chiral epoxide 5a epoxide, giving 2-naphthyl ketones. This process is ef-
bearing an S-oxiranyl configuration, as shown in ficient with 1,2,2-trisubstituted epoxides with a selec-
Scheme 4, we envisage that the oxiranyl group initial- tive 1,2-migration. The same reactions on epoxide
ꢀ
ly attacks at the CMe carbon to give eight-mem- substrates bearing a siloxy group gave bicyclic ketals
bered oxacyclic intermediate F.[12] A subsequent SN2- with high diastereoselectivity. This oxacyclization
type water attack is expected to give alcohol G with works efficiently with 1,1-disubsituted epoxides be-
a release of a proton. This proton assists the removal cause a tertiary cation is generated in key intermedi-
of the siloxy moiety to form an oxaallylic cation I to ate E.
induce an intramolecular cyclization to generate
chiral bicyclic ketal 6a. A similar transformation is
also applicable to the other diastereomer 5a bearing
an R-oxiranyl configuration that gives 6a in the oppo-
Experimental Section
site configuration (Scheme 5).
General Remarks
Unless otherwise noted, all reactions were carried out under
a nitrogen atmosphere in oven-dried glassware using stan-
dard syringe, cannula and septa apparatus. Benzene, diethyl
ether, tetrahydrofuran and hexane were dried with sodium,
benzophenone and distilled before use. Dichloromethane
was distilled over CaH2 before use. 1-(2-Bromophenyl)etha-
none was obtained commercially and used without purifica-
Conclusions
In summary, we report the oxy effects on the plati-
num-catalyzed cyclizations of 2-oxiranyl-1-(1-oxyalk-
2-ynyl)benzenes 3 and 5. For epoxide substrates bear-
ing an acyloxy group, their catalytic cyclizations pro- tion. All NMR spectra were run at 400/500/600 MHz
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Oxy Effects on the Platinum-Catalyzed Carbo- and Oxacyclizations
(1H NMR) or 100/125/150 MHz (13C NMR) in CDCl3/
Standard Procedure for Catalytic Operations:
Synthesis of Bicyclic Ketal 6a
CD2Cl2 solutions.
To a reaction flask was added PtCl2 (6.6 mg, 0.025 mmol)
before it was dried under vacuum at 258C for 10 min. To
this flask was charged CO and dichloroethane (1.0 mL), and
the mixture was stirred for 5 min before a dichloroethane
solution (3.0 mL) of epoxide 5a (100 mg, 0.36 mmol) and
water (6 mL, 0.36 mmol) was added. The resulting suspen-
sion was stirred for 25 min at room temperature before it
was concentrated, and eluted through a silica column
(hexane) to afford compound 6a as a yellow liquid; yield:
63.3 mg (0.31 mmol, 86%).
Synthesis of 1-[2-(3,3-Dimethyloxirane-2-yl)phenyl]-
but-2-ynyl Acetate (3a); Typical Procedure
Similar catalytic reactions were performed with 0.35–
0.40 mmol scale.
mCPBA (0.267 g, 1.5 mmol), and NaHCO3 (0.173 g,
2.0 mmol), were added to a DCM solution of I (0.25 g,
1.0 mmol)[13] and stirred for 5 h. The reaction was quenched
with water, extracted with DCM (25 mL). The extract was
washed with water, dried over MgSO4, and concentrated
under reduced pressure. The residue was eluted through
a silica column to afford compound 3a as a colorless liquid;
yield: 0.23 g (0.9 mmol, 87%).
Spectral Data
Spectral data for compounds 3a, 4a–4c, 4e–4h, 4j, 4k, 4m,
4n, 5a, 6a–6f and 6i–6m are listed below. Spectral data for
the remaining compounds, together with copies of the 1H
and 13C NMR spectra of all compounds, are given in the
Supporting Information.
1-[2-(3,3-Dimethyloxiran-2-yl)phenyl]but-2-ynyl acetate
1
(3a): H NMR [500 MHz, CDCl3; mixture of diastereomers
Synthesis of Trimethyl{1-[2-(2-methyloxiran-2-yl)-
phenyl]but-2-ynyloxy}silane(5a); Typical Procedure
(1/1.8)]: major isomer: 7.56–7.53 (m, 1H), 7.38–7.26 (m,
3H), 6.54 (q, J=3.0 Hz, 1H), 4.07–4.05 (m, 2H), 2.06 (s,
3H), 1.86 (d, J=2.0 Hz, 3H), 1.48 (s, 6H); minor isomer
(selected peaks): d=6.48 (q, J=2.5 Hz, 1H), 2.08 (s, 3H),
1.84 (d, J=2.5 Hz, 3H), 1.50 (s, 3H); 13C NMR (125 MHz,
CDCl3): d=169.6, 169.4, 135.1, 134.9, 134.8, 134.7, 128.6,
128.5, 127.7, 127.5, 127.3, 126.9, 126.8, 84.0, 83.7, 75.5, 75.4,
63.6, 63.5, 62.4, 62.3, 61.6, 61.2, 24.4, 24.3, 21.0, 20.9, 18.3,
18.0, 3.8, 3.7; IR (nujol): n=3033 (s), 2101 (s), 1720 (s),1588
(s), 1450 (s), 1255 (s), 1020 (s), 1150 (s), 888 (s), 810 cmÀ1
(s); HR-MS: m/z=258.1258, calcd. for C16H18O3: 258.1256.
1-(3,4-Dimethylnaphthalen-2-yl)ethanone (4a): 1H NMR
(400 MHz, CDCl3): d=8.02 (d, J=8.6 Hz, 1H), 7.89 (s, 1H),
7.82 (d, J=8.2 Hz, 1H), 7.55 (dt, J=7.6, 1.2 Hz, 1H), 7.45
(dt, J=7.8, 0.76 Hz, 1H), 2.66 (s, 3H), 2.61 (s, 3H), 2.51 (s,
3H); 13C NMR (100 MHz, CDCl3): d=203.8, 138.9, 133.7,
133.4, 130.7, 130.5, 129.1, 127.6, 126.5, 125.4, 123.8, 30.4,
17.4, 14.7; IR (nujol): n=3071 (s), 2805 (s), 1742 (s), 1595
(s), 1472 cmÀ1 (s); HR-MS: m/z=198.1043, calcd. for
C14H14O: 198.1045.
mCPBA (0.22 g, 1.2 mmol), and NaHCO3 (0.214 g,
2.5 mmol), were added to a DCM solution of II (0.22 g,
0.9 mmol)[12] and stirred for 5 h. The reaction was quenched
with water, then extracted with DCM (25 mL). The extract
was washed with water, dried over MgSO4, and concentrat-
ed under reduced pressure. The residue was eluted through
a silica column to afford compound 5a as a colorless liquid;
yield: 0.196 g (0.7 mmol, 84%).
1-(3,4-Dimethylnaphthalen-2-yl)butan-1-one
(4b):
Standard Procedure for Catalytic Operations:
Synthesis of 2-Naphthyl Ketone 4a
1H NMR (400 MHz, CDCl3): d=8.02 (d, J=8.6 Hz, 1H),
7.80 (d, J=8.2 Hz, 1H), 7.78 (s, 1H), 7.54 (dt, J=6.8,
1.4 Hz, 1H), 7.44 (dt, J=7.0, 1.0 Hz, 1H), 2.93 (t, J=7.3 Hz,
2H), 2.61 (s, 3H), 2.45 (s, 3H), 1.76 (q, J=7.4 Hz, 2H), 1.00
(t, J=7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=207.1,
139.6, 133.4, 133.3, 130.8, 130.2, 129.0, 127.3, 125.4, 125.3,
123.8, 44.8, 17.9, 17.3, 14.7, 13.8; IR (nujol): n=3070 (s),
2803 (s), 1744 (s), 1595 (s), 1478 cmÀ1 (s); HR-MS: m/z=
226.1360, calcd. for C16H18O: 226.1358.
To a reaction flask was added PtCl2 (10.3 mg, 0.038 mmol)
before it was dried under vacuum at 258C for 10 min. To
this flask was charged CO and dry dichloroethane (1.0 mL),
and the mixture was stirred for 5 min before a dichloro-
ethane solution (3.0 mL) of epoxide 3a (100 mg, 0.38 mmol)
was added. The resulting suspension was stirred for 1 h at
708C before it was concentrated, and eluted through a silica
column (hexane) to afford compound 4a as a yellow liquid;
yield: 62.2 mg (0.31 mmol, 81%).
(3,4-Dimethylnaphthalen-2-yl)
G
(4c):
1H NMR (400 MHz, CDCl3): d=8.08 (dd, J=8.5, 0.6 Hz,
1H), 7.86 (dd, J=8.0, 1.0 Hz, 2H), 7.78 (dd, J=7.6, 0.6 Hz,
1H), 7.65 (s, 1H), 7.60–7.54 (m, 2H), 7.47–7.43 (m, 3H),
2.66 (s, 3H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3): d=
199.1, 138.3, 137.8, 133.3, 133.2, 133.0, 130.7, 130.4, 130.2
(2ꢁCH), 128.9, 128.4 (2ꢁCH), 127.1, 126.0, 125.3, 123.8,
17.7, 14.6; IR (nujol) : n=3079 (s), 2804 (s), 1744 (s), 1592
Similar catalytic reactions were performed with 0.35–
0.40 mmol scale.
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(s), 1470 cmÀ1 (s); HR-MS: m/z=260.1204, calcd. for
C19H16O: 260.1201.
1471 cmÀ1 (s); HR-MS: m/z=216.0953, calcd. for C14H13FO:
216.0950.
1-(7-Methoxy-3,4-dimethylnaphthalen-2-yl)ethanone
(4m): 1H NMR (600 MHz, CDCl3): d=7.93 (d, J=9.3 Hz,
1H), 7.78 (s, 1H), 7.21 (dd, J=9.3, 2.7 Hz, 1H), 7.11 (d, J=
2.7 Hz, 1H), 3.90 (s, 3H), 2.64 (s, 3H), 2.57 (s, 3H), 2.46 (s,
3H); 13C NMR (150 MHz, CDCl3): d=204.1, 157.1, 139.5,
133.4, 131.9, 129.2, 128.1, 125.5, 125.2, 120.1, 106.7, 55.3,
30.5, 17.1, 14.8; IR (nujol): n=3073 (s), 2806 (s), 1749 (s),
1595 (s), 1472 cmÀ1 (s); HR-MS: m/z=228.1151, calcd. for
C15H16O2: 228.1150.
1-(3-Methyl-4-propylnaphthalen-2-yl)ethanone
(4e):
1H NMR (400 MHz, CDCl3): d=8.00 (d, J=8.6 Hz, 1H),
7.89 (s, 1H), 7.82 (d, J=8.2 Hz, 1H), 7.54 (dt, J=6.7,
1.2 Hz, 1H), 7.44 (t, J=7.0 Hz, 1H), 3.08–3.03 (m, 2H), 2.65
(s, 3H), 2.51 (s, 3H), 1.66–1.59 (m, 2H), 1.08 (t, J=7.4 Hz,
3H); 13C NMR (100 MHz, CDCl3): d=203.9, 139.0, 138.0,
133.1, 131.0, 130.1, 129.2, 127.6, 126.7, 125.3, 123.9, 30.7,
30.4, 23.2, 16.8, 14.6; IR (nujol): n=3070 (s), 2803 (s), 1744
(s), 1595 (s), 1478 cmÀ1 (s); HR-MS: m/z=226.1359, calcd.
for C16H18O: 226.1358.
1-(7,8-DimethylnaphthoACTHNUTRGENNU[G 2,3-d]ACHTUNGTERN[NUGN 1,3]dioxol-6-yl)ethanone
1
(4n): H NMR (600 MHz, CDCl3): d=7.73 (s, 1H), 7.31 (s,
1H), 7.08 (s, 1H), 6.04 (s, 2H), 2.62 (s, 3H), 2.50 (s, 3H),
2.47 (s, 3H); 13C NMR (150 MHz, CDCl3): d=203.6, 149.3,
147.0, 137.2, 133.1, 132.5, 131.3, 127.5, 125.9, 104.7, 101.2,
100.7, 30.3, 17.3, 15.3; IR (nujol): n=3070 (s), 2809 (s), 1752
(s), 1590 (s), 1477 cmÀ1 (s); HR-MS: m/z=242.0946, calcd.
for C15H14O3: 242.0943.
1-(3-Methyl-4-phenylnaphthalen-2-yl)ethanone
(4f):
1H NMR (400 MHz, CDCl3): d=8.12 (s, 1H), 7.87 (d, J=
7.8 Hz, 1H), 7.51–7.36 (m, 5H), 7.30 (d, J=8.2 Hz, 1H),
7.23–7.21 (m, 2H), 2.72 (s, 3H), 2.27 (s, 3H); 13C NMR
(100 MHz, CDCl3): d=203.0, 140.4, 139.4, 138.1, 134.1,
131.0, 130.7, 130.0 (2ꢁCH), 128.5 (4ꢁCH), 127.7, 127.2,
126.4, 125.6, 30.2, 18.6; IR (nujol): n=3075 (s), 2800 (s),
1744 (s), 1590 (s), 1478 cmÀ1 (s); HR-MS: m/z=260.1202,
calcd. for C19H16O: 260.1201.
Trimethyl{1-[2-(2-methyloxiran-2-yl)phenyl]but-2-ynyl-
1
oxy}silane (5a): H NMR [400 MHz, CD2Cl2; mixture of dia-
stereomers (1/1.4)]: d=7.67 (dd, J=3.8, 1.7 Hz, 2H), 7.38–
7.25 (m, 6H), 5.89 (q, J=2.1 Hz, 1H), 5.80 (q, J=2.1 Hz,
1H), 2.97–2.94 (m, 2H), 2.92 (da,b, J=5.4 Hz, 1H), 2.85 (da,b,
J=5.4 Hz, 1H), 1.85 (d, J=2.1 Hz, 3H), 1.84 (d, J=2.1 Hz,
3H), 1.64 (s, 6H), 0.20 (s, 9H), 0.19 (s, 9H);13C NMR
(100 MHz, CDCl3): d=139.8, 139.3, 137.8, 137.3, 128.0 (2ꢁ
CH), 127.8, 127.6, 127.3, 127.2, 127.1, 126.9, 82.5, 82.3, 80.3,
80.1, 61.4, 61.1, 58.0, 57.8, 55.1, 54.8, 24.8, 24.6, 3.7 (2ꢁCH3),
0.3 (3ꢁCH3), 0.2 (3ꢁCH3); IR (nujol): n=3035 (s), 2105 (s),
1582 (s), 1450 (s), 1262 (s), 1253 (s), 1150 (s), 1022 (s), 890
(s), 810 cmÀ1 (s); HR-MS: m/z=274.1390, calcd. for
C16H22O2Si: 274.1389.
1-(5,6,7,8-Tetrahydrophenathrene-9-yl)ethanone
(4g):
1H NMR (400 MHz, CDCl3): d=7.97 (d, J=8.6 Hz, 1H),
7.94 (s, 1H), 7.82 (d, J=7.9 Hz, 1H), 7.56 (dt, J=6.9,
1.4 Hz, 1H), 7.46 (t, J=7.0 Hz, 1H), 3.13 (t, J=6.3 Hz, 2H),
3.02 (t, J=6.2 Hz, 2H), 2.65 (s, 3H), 1.95–1.90 (m, 2H),
1.83–1.77 (m, 2H); 13C NMR (100 MHz, CDCl3): d=203.0,
137.9, 133.7, 133.3, 132.4, 130.5, 129.2, 127.8, 127.3, 125.5,
122.8, 30.2, 28.5, 26.4, 22.9, 22.5; IR (nujol): n=3077 (s),
2808 (s), 1747 (s), 1592 (s), 1471 cmÀ1 (s); HR-MS: m/z=
224.1201,calcd. for C16H16O: 224.1201.
1-(3-Butylnaphthalen-2-yl)pentan-1-one (4h): 1H NMR
(600 MHz, CDCl3): d=8.04 (s, 1H), 7.83 (d, J=8.1 Hz, 1H),
7.76 (d, J=8.1 Hz, 1H), 7.64 (s, 1H), 7.50 (dt, J=6.6,
1.1 Hz, 1H), 7.44 (dt, J=8.1, 1.1 Hz, 1H), 2.99 (t, J=7.5 Hz,
2H), 2.93 (t, J=7.8 Hz, 2H), 1.73–1.64 (m, 2H), 1.59–1.57
(m, 2H), 1.43–1.36 (m, 4H), 0.94 (t, J=7.2 Hz, 3H), 0.91 (t,
J=7.3 Hz, 3H); 13C NMR (150 MHz, CDCl3): d=205.3,
138.8, 137.5, 134.3, 130.9, 129.0, 128.6, 128.2, 127.6, 127.1,
125.8, 41.9, 33.9, 33.5, 26.6, 22.7, 22.4, 14.0, 13.9; IR (nujol):
n=3070 (s), 2809 (s), 1741 (s), 1595 (s), 1475 cmÀ1 (s); HR-
MS: m/z=268.1828, calcd. for C19H24O: 268.1827.
1
Compound 6a: H NMR (400 MHz, CDCl3): d=7.30–7.21
(m, 4H), 6.50 (d, J=11.8 Hz, 1H), 5.79 (d, J=11.8 Hz, 1H),
3.94 (da,b, J=8.2 Hz, 1H), 3.81 (da,b, J=8.2 Hz, 1H), 1.79 (s,
3H), 1.65 (s, 3H); 13C NMR (100 MHz, CDCl3): d=144.4,
134.0, 133.0, 131.8, 131.3, 127.7, 127.6, 124.7, 107.8, 80.9,
76.5, 25.3, 23.0; IR (nujol): n=3070 (s), 2805 (s), 1582 (s),
1472 (s), 1021 cmÀ1 (s); HR-MS: m/z=202.0996, calcd. for
C13H14O2: 202.0994.
1
Compound 6b: H NMR (400 MHz, CDCl3): d=7.30–7.18
(m, 4H), 6.50 (d, J=11.8 Hz, 1H), 5.80 (d, J=11.8 Hz, 1H),
3.94 (da,b, J=7.8 Hz, 1H), 3.79 (da,b, J=7.8 Hz, 1H), 1.89–
1.84 (m, 2H), 1.77 (s, 3H), 1.60–1.53 (m, 2H; s, 3H), 0.95 (t,
J=7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): d=144.6,
134.2, 133.0, 131.7, 131.6, 127.6, 127.5, 124.7, 109.4, 80.6,
76.3, 38.3, 25.1, 16.6, 14.4; IR (nujol) : n=3069 (s), 2801 (s),
1580 (s), 1475 (s), 1022 cmÀ1 (s); HR-MS: m/z=230.1310,
calcd. for C15H18O2: 230.1307.
1-(6-Fluoro-3,4-dimethylnaphthalen-2-yl)ethanone
(4j):
1H NMR (400 MHz, CDCl3): d=7.87 (s, 1H), 7.78 (dd, J=
8.9, 6.0 Hz, 1H), 7.58 (dd, J=9.2, 2.4 Hz, 1H), 7.21 (dt, J=
8.3, 2.5 Hz, 1H), 2.64 (s, 3H), 2.51 (s, 3H), 2.49 (s, 3H);
13C NMR (100 MHz, CDCl3): d=203.2, 161.9 (d, JC,F
245.0 Hz), 138.1, 134.8 (d, JC,F =9.0 Hz), 132.7 (d, JC,F
=
=
5.0 Hz), 131.5 (d, JC,F =9.0 Hz), 127.6 (2ꢁC), 126.4, 115.6 (d,
C,F =25.0 Hz), 107.7 (d, JC,F =22.0 Hz), 30.2, 17.4, 14.8; IR
1
J
Compound 6c: H NMR (400 MHz, CD2Cl2): d=7.32–7.20
(nujol): n=3071 (s), 2805 (s), 1742 (s), 1595 (s), 1472 cmÀ1
(s); HR-MS: m/z=216.0951, calcd. for C14H13FO: 216.0950.
1-(7-Fluoro-3,4-dimethylnaphthalen-2-yl)ethanone (4k):
1H NMR (400 MHz, CDCl3): d=7.99 (dd, J=9.3, 5.4 Hz,
1H), 7.76 (s, 1H), 7.40 (dd, J=9.3, 2.3 Hz, 1H), 7.29 (dt, J=
8.4, 2.6 Hz, 1H), 2.63 (d, J=0.8 Hz, 3H), 2.57 (s, 3H), 2.46
(s, 3H); 13C NMR (100 MHz, CDCl3): d=203.8, 160.1 (d,
(m, 4H), 6.49 (d, J=11.6 Hz, 1H), 5.81 (d, J=11.6 Hz, 1H),
3.85 (da,b, J=8.4 Hz, 2H), 2.19–2.12 (m, 1H), 2.05–1.98 (m,
1H), 1.54 (s, 3H), 1.52–1.43 (m, 4H), 0.99 (t, J=7.2 Hz,
3H); 13C NMR (150 MHz, CD2Cl2): d=145.7, 135.5, 133.9,
133.0, 132.0, 128.2, 128.1, 125.7, 108.4, 83.6, 75.9, 37.4, 25.8,
24.0, 23.2, 14.7; IR (nujol): n=3065 (s), 2809 (s), 1582 (s),
1475 (s), 1020 cmÀ1 (s); HR-MS: m/z= 244.1465, calcd. for
C16H20O2: 244.1463.
J
C,F =245.0 Hz), 140.1, 133.6, 131.6 (d, JC,F =9.0 Hz), 130.6,
Compound 6d: 1H NMR (400 MHz, CD2Cl2): d=7.32–
7.19 (m, 4H), 6.51 (d, J=11.7 Hz, 1H), 5.85 (d, J=11.7 Hz,
1H), 4.16 (q, J=6.3 Hz, 1H), 1.60 (s, 3H), 1.57 (s, 3H), 1.19
129.6, 126.4 (d, JC,F =8.0 Hz), 125.2 (d, JC,F =5.0 Hz), 117.5
(d, JC,F =24.0 Hz), 111.8 (d, JC,F =20.0 Hz), 30.4, 17.2, 14.9;
IR (nujol): n=3072 (s), 2804 (s), 1742 (s), 1595 (s),
2248
asc.wiley-vch.de
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2012, 354, 2241 – 2250

Oxy Effects on the Platinum-Catalyzed Carbo- and Oxacyclizations
(d, J=6.3 Hz, 3H); 13C NMR (150 MHz, CD2Cl2): d=146.8,
135.1, 133.8, 133.7, 132.0, 128.3, 128.2, 125.5, 105.4, 83.1,
79.9, 23.9, 21.3, 15.3; IR (nujol): n=3070 (s), 2810 (s), 1584
(s), 1473 (s), 1021 cmÀ1 (s); HR-MS: m/z=216.1155, calcd.
for C14H16O2: 216.1150.
1H), 3.89 (da,b, J=8.2 Hz, 1H), 3.80 (s, 3H), 3.78 (da,b, J=
8.2 Hz, 1H), 1.74 (s, 3H), 1.59 (s, 3H); 13C NMR (150 MHz,
CD2Cl2): d=159.7, 147.2, 134.9, 131.3, 130.0, 127.8, 113.0,
111.7, 108.7, 81.4, 77.1, 56.0, 25.8, 23.7; IR (nujol): n=3074
(s), 2800 (s), 1578 (s), 1477 (s), 1039 cmÀ1 (s); HR-MS:
m/z=232.1102, calcd. for C14H16O2: 232.1099.
Compound 6e: 1H NMR (400 MHz, CD2Cl2) : d=7.33–
7.22 (m, 4H), 6.52 (d, J=11.7 Hz, 1H), 5.86 (d, J=11.7 Hz,
1H), 3.90 (dd, J=9.0, 4.4 Hz, 1H), 1.61 (s, 3H), 1.59 (s,
3H), 1.58–1.57 (m, 2H), 0.91 (t, J=7.4 Hz, 3H); 13C NMR
(150 MHz, CD2Cl2): d=147.1, 135.1, 133.8, 133.7, 132.0,
128.1, 128.0, 126.1, 105.3, 82.5, 81.5, 23.9, 23.5, 21.2, 11.8; IR
(nujol): n=3077 (s), 2811 (s), 1581 (s), 1475 (s), 1026 cmÀ1
(s); HR-MS: m/z=230.1309, calcd. for C15H18O2: 230.1307.
Acknowledgements
The authors wish to thank the National Science Council,
Taiwan, and the Ministry of Education, Taiwan for support
of this work.
1
Compound 6f: H NMR (600 MHz, CD2Cl2): d=7.35–7.25
(m, 4H), 6.57 (d, J=11.7 Hz, 1H), 5.88 (d, J=11.7 Hz, 1H),
4.20 (q, J=6.4 Hz, 1H), 1.86–1.81 (m, 2H), 1.62 (s, 3H),
1.58–1.53 (m, 2H), 1.22 (d, J=6.4 Hz, 3H), 0.99 (t, J=
7.4 Hz, 3H); 13C NMR (150 MHz, CD2Cl2): d=146.8, 135.2,
133.8, 133.4, 132.3, 128.1, 128.0, 125.5, 106.9, 82.8, 79.6, 39.2,
21.1, 17.3, 15.3, 14.9; IR (nujol): n=3072 (s), 2814 (s), 1580
(s), 1475 (s), 1027 cmÀ1 (s); HR-MS: m/z=244.1466, calcd.
for C16H20O2: 244.1463.
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1
Compound 6i: H NMR (400 MHz, CD2Cl2): d=7.28 (dd,
J=6.5, 5.7 Hz, 1H), 7.02 (dd, J=9.7, 2.7 Hz, 1H), 6.94–6.90
(m, 1H), 6.43 (d, J=11.8 Hz, 1H), 5.86 (d, J=11.8 Hz, 1H),
3.87 (da,b, J=8.2 Hz, 1H), 3.80 (da,b, J=8.2 Hz, 1H), 1.76 (s,
3H), 1.61 (s, 3H); 13C NMR (150 MHz, CD2Cl2): d=162.6
(d, JC,F =243.6 Hz), 141.6, 134.3, 130.7, 127.3, 127.2, 119.8 (d,
J
C.F =21.9 Hz), 114.2 (d, JC.F =20.8 Hz), 108.3, 81.2, 77.2,
26.1, 23.9; IR (nujol): n=3073 (s), 2800 (s), 1587 (s), 1474
(s), 1026 cmÀ1 (s); HR-MS: m/z=220.0904, calcd for
C13H13FO2: 220.0900.
1
Compound 6j: H NMR (600 MHz, CD2Cl2): d=7.33 (dd,
J=8.4, 5.9 Hz, 1H), 7.08 (dd, J=10.2, 2.6 Hz, 1H), 7.01–
6.99 (m, 1H), 6.51 (d, J=11.8 Hz, 1H), 5.80 (d, J=11.8 Hz,
1H), 3.94 (da,b, J=8.3 Hz, 1H), 3.84 (da,b, J=8.3 Hz, 1H),
1.78 (s, 3H), 1.64 (s, 3H); 13C NMR (150 MHz, CD2Cl2): d=
162.6 (d, JC,F =246.6 Hz), 148.2 (d, JC,F =6.4 Hz), 135.2 (d,
J
C,F =8.2 Hz), 132.0, 131.3, 130.7, 114.6 (d, JC,F =21.1 Hz),
113.3 (d, JC,F =23.2 Hz), 108.8, 81.1, 77.0, 25.8, 23.6; IR
(nujol): n=3072 (s), 2801 (s), 1586 (s), 1474 (s), 1025 cmÀ1
(s); HR-MS: m/z=220.0904, calcd. for C13H13FO2: 220.0900.
1
Compound 6k: H NMR (400 MHz, CD2Cl2): d=7.30 (d,
J=2.1 Hz, 1H), 7.25 (d, J=8.3 Hz, 1H), 7.20 (dd, J=8.4,
2.2 Hz, 1H), 6.42 (d, J=11.7 Hz, 1H), 5.86 (d, J=11.7 Hz,
1H), 3.86 (da,b, J=8.2 Hz, 1H), 3.80 (da,b, J=8.2 Hz, 1H),
1.75 (s, 3H), 1.61 (s, 3H); 13C NMR (100 MHz, CD2Cl2): d=
143.7, 136.4, 134.0, 133.4, 132.6, 130.1, 127.4, 126.6, 108.0,
80.8, 76.7, 25.5, 23.1; IR (nujol): n=3071 (s), 2806 (s), 1581
(s), 1473 (s), 1031 cmÀ1 (s); HR-MS: m/z=236.0602, calcd.
for C13H13ClO2: 236.0604.
Compound 6l: 1H NMR (400 MHz, CD2Cl2): d=7.29 (s,
1H), 7.25 (d, J=1.4 Hz, 2H), 6.47 (d, J=11.8 Hz, 1H), 5.81
(d, J=11.8 Hz, 1H), 3.88 (da,b, J=8.3 Hz, 1H), 3.80 (da,b, J=
8.3 Hz, 1H), 1.75 (s, 3H), 1.61 (s, 3H); 13C NMR (100 MHz,
CD2Cl2): d=143.7, 136.4, 134.0, 133.4, 132.6, 130.1, 127.4,
126.6, 108.0, 80.8, 76.7, 25.5, 23.1; IR (nujol): n=3072 (s),
2804 (s), 1580 (s), 1473 (s), 1033 cmÀ1 (s); HR-MS: m/z=
236.0602, calcd. for C13H13ClO2: 236.0604.
1
Compound 6m: H NMR (400 MHz, CD2Cl2): d=7.23 (d,
J=8.4 Hz, 1H), 6.86 (d, J=2.6 Hz, 1H), 6.77 (dd, J=8.4,
2.6 Hz, 1H), 6.45 (d, J=11.7 Hz, 1H), 5.65 (d, J=11.7 Hz,
Adv. Synth. Catal. 2012, 354, 2241 – 2250
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
2249

Rupsha Chaudhuri et al.
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