Palladium-catalyzed highly chemo-, regio- and stereoselective synthesis of eight- to ten-membered lactones from allenyl 3-oxoalkanoates and organic halides

Article abstract of DOI:10.1002/adsc.201100075

A highly chemo-, regio-, and stereoselective synthesis of eight- to ten-membered lactones via the coupling cyclization of readily available allenyl 3-oxoalkanoates and organic halides through an anti-π-allylic palladium intermediate is reported. The yield

Full text of DOI:10.1002/adsc.201100075

FULL PAPERS
DOI: 10.1002/adsc.201100075
Palladium-Catalyzed Highly Chemo-, Regio- and Stereoselective
Synthesis of Eight- to Ten-Membered Lactones from Allenyl
3-Oxoalkanoates and Organic Halides
Baoqiang Wan,a Guochen Jia,b,* and Shengming Maa,c,*
a
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Linglin Lu, Shanghai 200032, Peopleꢀs Republic of China
Fax : (+86)-21-6416-7510; e-mail: masm@sioc.ac.cn
Department of Chemistry, the Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong,
b
Peopleꢀs Republic of China
Fax : (+852)-2358-1594; e-mail: chjiag@ust.hk
Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China Normal
c
University, 3663 North Zhongshan Lu, Shanghai 200062, Peopleꢀs Republic of China
Received: January 28, 2011; Revised: April 14, 2011; Published online: June 30, 2011
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adcs.201100075.
Abstract: A highly chemo-, regio-, and stereoselec- allylic palladium intermediate is reported. The yields
tive synthesis of eight- to ten-membered lactones via ranged from moderate to good.
the coupling cyclization of readily available allenyl 3-
oxoalkanoates and organic halides through an anti-p- Keywords: allenes; p-allylic intermediates; carbopal-
ladation; cyclization; lactones
Introduction
are difficult to synthesize not only by biosynthesis but
also by artificial synthetic technology due to entropic
Medium-sized lactones are extremely important com- and enthalpic factors.[3] Up to now, the most useful
pounds since they may be found in many natural methodologies used to construct medium-sized lac-
products with biological potential,[1] including octalac- tones are lactonization[1a,4] and ring-closing metathesis
tin B,[2a] obtained from the surface of the Sea of (RCM),[5] usually requiring high diluted conditions,
Cortez gorgonian octocoral Pacifigorgia sp., and hali- thus, the synthesis of medium-sized lactones is still a
cholactone,[2b] a novel fatty acid metabolite from the formidable challenge.
marine sponge, and ascidiatrienolide A[2c] (Figure 1).
Recently, transition metal-catalyzed cyclization re-
It is well-known that medium-sized ring compounds actions of functionalized allenes in the presence of or-
ganic halides have become powerful tools for the syn-
thesis of carbo- and heterocyclic compounds.[6,7]
Cyclic carbopalladation has been reported to afford
8- to 12-membered rings.[8] An intermolecular carbo-
palladation-allylation protocol of alkenyl halides bear-
ing a nucleophilic moiety afforded 8-membered rings
with 62:38 to 92:8 stereoselectivity.[9] In addition,
Trost and co-workers reported the synthesis of 9- to
17-membered rings via hydropalladation of allenes
under highly diluted conditions.[10] On the basis of our
previous work on the carbopalladation of allenes[7]
forming cyclic compounds with malonate or amine as
the nucleophilic moiety,[11] we envisioned that the car-
bopalladation of allenyl 3-oxoalkanoate 1a [from the
Figure 1. Natural eight- to ten-membered lactones.
reaction of readily available b-methylene-b-lactone
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Scheme 1. Synthesis of the starting materials 1a–1m.
Scheme 2. Possible products of the reaction of allenyl 3-oxoalkanoate 1a with iodobenzene.
and the allenic alcohol or ester exchange reaction of membered ring over the 6-membered ring with the
3-oxoalkanoates with 3,4-pentadienol (Scheme 1)][12] exclusive C-attack.
may form six-, eight-, or even ten-membered lactones
4a, 2a, 5a, and 3a, respectively with the C-attack[13] or
O-attack[14] of the p-allylic palladium intermediate Results and Discussion
due to the presence of the keto ester unit (Scheme 2).
It has been reported that in the absence of the sub- When we heated allene 1a, PhI (1.5 equiv.), and
stituent at the 2-position syn-p-allylic palladium is fa- K2CO3 (2.0 equiv.) in the presence of PdACHTUNGTRENNUNG(PPh3)4
vored.[15] Herein, we wish to describe a highly effi- (5 mol%) in CH3CN at 858C for 46 h (Table 1,
cient chemo-, regio-, and stereoselective protocol to entry 1), interestingly, the formation of the most fa-
construct eight- to ten-membered lactones via carbo- vored six-membered C-attack lactone 4a should be
palladation of readily available allenyl 3-oxoalkano- <2% by NMR, if any. In addition, it should be noted
ACHTUNGTRENNUNG
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Palladium-Catalyzed Highly Chemo-, Regio- and Stereoselective Synthesis of Eight- to Ten-Membered Lactones
Table 1. The effects of catalyst and temperature on the Pd-
catalyzed coupling-cyclization of 1a with PhI.[a]
Table 2. Solvent and base effects in the Pd-catalyzed cou-
pling-cyclization of 1a with PhI.[a]
Entry Base
Solvent Time Recovery of Yield of
Entry Catalyst (mol%)
T
Time Yield of
1a [%][b]
2a [%][b]
[oC] [h]
2a [%][b]
[h]
1
2
3
4
5
6
7
8
K2CO3 CH3CN
K2CO3 toluene 26
6
0
25
22
81
42
59
42
68
27
8
16
20
28
trace
1
2
3
4
Pd
Pd
Pd
Pd
G
85
85
46
6
6
66
81 (75)[c]
64[d]
K2CO3 THF
K2CO3 DCE
K2CO3 CH3NO2 24
Na2CO3 CH3CN 34
Cs2CO3 CH3CN 11
26
21.7
69[e]
30.5 28
0
55
0
[a]
Under argon,
(0.375 mmol), K2CO3 (2 equiv.), the palladium catalyst
(5 mol%), and ligand in 2 mL of CH3CN was stirred at
the indicated temperature.
Et3N
CH3CN 46.5 39
9
10
11
KOH
CH3CN 15.5
0
0
[b]
[c]
The yield was determined by 1H NMR analysis using
1,3,5-trimethylbenzene as the internal standard.
The number shown in the parenthesis is the isolated
yield.
K3PO4 CH3CN 15.5
CaH2
CH3CN 45.5 16
[a]
[b]
The reaction was carried out with 1a (0.250 mmol), PhI
(0.375 mmol), Pd(OAc)2 (5 mol%), PPh3 (10 mol%), and
[d]
[e]
AHCTUNGTRENNUNG
5% of the starting material 1a remained.
14% of the starting material 1a remained.
base (2 equiv.) in solvent (2 mL). THF=tetrahydrofuran,
DCE=1,2-dichloroethane.
Determined by 1H NMR analysis using 1,3,5-trimethyl-
benzene as the internal standard.
form C-attack eight-membered lactone 2a was formed
With the optimal conditions in hand, firstly, the
and isolated as the only product with a very high scope of functionalized allenes was investigated.
chemo- and regioselectivity.
Changing the R1 group, the reaction proceeded to
A screening of palladium catalysts was then per- afford the desired lactones in good yields (Table 3, en-
formed, and it was found that the reaction proceeded tries 2 and 3). Notably, the reaction of more sterically
smoothly with PdACHTNUGTRNEUNG(OAc)2 (5 mol%) and PPh3 hindered allenyl 2-substituted-3-oxoalkanoates also
(10 mol%) within a short period of time affording 2a afforded the corresponding lactones in good to mod-
in 75% isolated yield and the formation of 4a should erate yields, in which a quaternary carbon was con-
be <2.3% by NMR, if any. (Table 1, entry 2). Short- structed. It is interesting to observe that the R2 sub-
ening the reaction time to 90 min, we only detected stituent has a dramatic effect on the reaction time.
the C-attack product 2a in 59% yield and 29% recov- From methyl to Bn to allyl to ethyl or propyl, the re-
ery of 1a by NMR. The O-attack product was not ob- action requires a much longer time (Table 3, en-
served. Lowering the temperature to 508C, the reac- tries 4–7).
tion became sluggish with 14% of 1a remaining.
Then the standard conditions were applied to inves-
A subsequent comprehensive study of the solvent tigate the reaction of different organic halides with
effect indicated that the reaction can afford product 1c. The results are summarized in Table 4. Electron-
2a in all the tested solvents (Table 2, entries 1–5) with rich (Table 4, entries 1–5), electron-deficient (Table 4,
CH3CN (Table 1, entry 1) being the best. The base entry 6), Br-substituted (Table 4, entry 7) aryl iodides
effect using CH3CN as solvent was then investigated: and 3-thienyl iodide (Table 4, entry 8) all afforded the
The reaction afforded the desired product 2a in rela- corresponding eight-membered lactones in moderate
tively lower yields with Na2CO3, Cs2CO3, Et3N, KOH, to good yields. In addition, 1-hexenyl iodide (Table 4,
K3PO4, and CaH2 (Table 2, entries 6–11). Thus, the entry 9) and styryl iodide (Table 4, entry 10) may also
following reaction conditions [organic halide be used. The structures of all the eight-membered lac-
(1.5 equiv.), PdACHTUNGTRENNUNG(OAc)2 (5 mol%), PPh3 (10 mol%), tones were assigned by analogy to that of 2m, which
K2CO3 (2.0 equiv.), MeCN, 858C] were defined as the was determined by a single crystal X-ray diffraction
standard for the coupling cyclization.
study (Figure 2).[16]
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Table 3. Substrate variation of compounds 1.[a]
Table 4. Coupling cyclization of 1c with different organic
halides.[a]
Entry
1
Time [h] Yield of 2 [%][b]
Entry
R
Time [h]
Yield of 2 [%][b]
R1 R2
1
2
3
4
5
6
7
8
9
4-MeC6H4
4-MeOC6H4
3-MeC6H4
3,4-Me2C6H3
3,4-(OCH2)2C6H3
4-EtO2CC6H4
4-BrC6H4
3-thienyl
1-(E)-hexenyl
(E)-styryl
2
5
2
1.6
2.5
3
3.5
2
75 (2g)
69 (2h)
78 (2i)
72 (2j)
66 (2k)
58 (2l)
63 (2m)
70 (2n)
59 (2o)
58 (2p)
1
2
3
4
4
5
6
7
Me H (1a)
i-Pr H (1b)
Ph H (1c)
Me Me (1d)
Me Bn (1j)
Me Et (1e)
Me n-Pr (1i)
4.5
6
1.5
10.5
22
73 (2a)
83 (2b)
79 (2c)
81 (2d)[c]
75 (2w)[c]
63 (2e)[c,d]
67 (2v)[c,d]
69 (2f)[c]
81.5
82
Me CH2=CHCH2 (1f) 29
2.5
1.5
[a]
10
The reaction was carried out with 1 (0.50 mmol), PhI
(0.75 mmol), Pd(OAc)2 (5 mol%), PPh3 (10 mol%), and
ACHTUNGTRENNUNG
[a]
The reaction was carried out with 1c (0.50 mmol), RI
(0.75 mmol), Pd(OAc)2 (5 mol%), PPh3 (10 mol%), and
K2CO3 (2 equiv.) in 4 mL of CH3CN.
Isolated yield.
The reaction was carried out at 1008C.
2.5 equiv. of PhI were used.
AHCTUNGTRENNUNG
[b]
[c]
[d]
K2CO3 (2 equiv.) in 4 mL of CH3CN.
Isolated yield.
[b]
The efficiency by which eight-membered lactones
formed prompted us to explore the possibility of syn-
thesizing other lactones. To our delight, this set of
standard conditions has been proven to be operative
for the efficient synthesis of nine- and ten-membered
lactones with highly chemo-, regio- and stereoselectiv-
ity (Scheme 3). The reaction of 1g with 1-iodo-4-nitro-
benzene gave the expected product E-2s in a satisfac-
tory yield of 74%. The structure of E-2s was further
established by single crystal X-ray diffraction study
(Figure 3).[17] In addition, the ten-membered lactone
E-2u[18] was obtained in 69% yield as a single stereo-
isomer and the configuration of C=C bond in this
compound was established by single crystal X-ray dif-
Figure 2. ORTEP representation of 2m.
Scheme 3. Synthesis of nine- and ten-membered lactones.
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Palladium-Catalyzed Highly Chemo-, Regio- and Stereoselective Synthesis of Eight- to Ten-Membered Lactones
Figure 3. ORTEP representations of E-2s and E-2u.
fraction study (Figure 3). The reaction of 1g with io- Scheme 5, obviously, the existence of the phenyl
dobenzene afforded the product 2q on a one-gram group strongly favors the formation of the p-allylic
scale in 82% yield.
palladium intermediate anti-6 rather than syn-6 to
In addition, we investigated some other allenyl 3- avoid the steric congestion between the phenyl group
oxoalkanoates. To our delight, the reaction of 1k with and the chain bearing the nucleophilic functionali-
1-iodo-4-nitrobenzene gave lactone 2x in 65% yield ty.[15,20] Subsequent highly chemoselective carbon nu-
and >8:1 dr (Scheme 4).[19] The structure of trans-2x cleophilic attack[13,14] to the p-allylic species at the less
was further established by a single crystal X-ray dif- substituted terminal affords the stereodefined eight-
fraction study (Figure 4). However, the reactions of 1l membered lactone 2a.
and 1m bearing substitutents at the allene moiety
with iodobenzene failed to afford the expected corre-
sponding eight-membered lactones (Scheme 4).
A rationale is proposed to explain the high regio-
Conclusions
and stereoselectivity using the reaction of 1a and io- In conclusion, we have developed a highly chemo-,
dobenzene as the example.[11] As illustrated in regio-, and stereoselective methodology for the syn-
Scheme 4. Coupling cyclization of some other substituted allenyl 3-oxoalkanoates.
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Experimental Section
General Information
All reactions were carried out in oven-dried Schlenk tubes.
CH3CN was dried over calcium hydride before distillation.
All the temperatures are referred to the oil baths used. The
petroleum ether was distilled before use.
Typical Procedure for the Preparation of 2
To a flame-dried Schlenk tube were added PdACHTUNGTRENNUNG(OAc)2
(5.7 mg, 0.025 mmol), PPh3 (13.3 mg, 0.050 mmol), K2CO3
(138.3 mg, 1.0 mmol), CH3CN (2 mL), iodobenzene
(153.6 mg, 0.75 mmol), CH3CN (1 mL), 1a (83.2 mg,
0.50 mmol), and 1 mL of CH3CN sequentially under argon.
The mixture was stirred at 858C in a preheated oil bath and
monitored by TLC. Upon completion, the resulting mixture
was filtered through a short column of silica gel and concen-
trated. The residue was purified by chromatography on
silica gel [eluent: petroleum ether (b.p. 30–608C)/ethyl
ether=10/1] to afford 3-acetyl-5-phenyl-5(E)-3,4,7,8-tetrahy-
dro-2H-oxocin-2-one (2a) as an oil; yield: 88.6 mg (73%).
1H NMR (300 MHz, CDCl3): d=7.39–7.18 (m, 5H, Ar-H),
5.95 (t, J=8.0 Hz, 1H, =CH), 4.54 (t, J=11.3 Hz, 1H, one
proton from OCH2), 4.25–4.10 (m, 1H, one proton from
OCH2), 3.55 (dd, J1 =11.7 Hz, J2 =3.9 Hz, 1H, O2CCH), 3.38
[t, J=12.3 Hz, 1H, one proton from C=C(Ph)CH2], 2.91–
2.68 [m, 2H, one proton from C=C(Ph)CH2 and one proton
from PhC=CCH2], 2.34–2.12 (m, 4H, one proton from PhC=
Figure 4. ORTEP representation of 2x.
thesis of normally difficult-to-form eight- to ten-mem-
bered lactones by palladium-catalyzed carbon-carbon CCH2 and CH3); 13C NMR (75.4 MHz, CDCl3): d=200.7,
173.0, 142.5, 142.1, 128.3, 127.4, 126.4, 126.3, 68.7, 63.4, 30.8,
29.8, 28.7; IR (neat): n=2958, 1750, 1718, 1491, 1460, 1363,
1317, 1257, 1205, 1145, 1103, 1046, 1028, 1004 cmꢀ1; MS (70
eV, EI): m/z (%)=244 (M+, 10.87), 43 (100); HR-MS:
m/z=244.1098, calcd. for C15H16O3 (M+): 244.1099.
bond formation via the coupling cyclization of allenyl
alkanoates with organic halides. Owing to the readily
available nature of b-methylene-b-lactone,[12] the alle-
nols[21] and organic halides (Scheme 1) and the impor-
tance of the lactone skeleton, the reaction will be po-
tentially useful in organic synthesis and medicinal
chemistry. In addition, the observed exclusive C-
attack is also quite interesting. Further studies in this
area are on going in our laboratory.
Synthesis of 3-Isobutyryl-5-phenyl-5(E)-3,4,7,8-tetra-
hydro-2H-oxocin-2-one (2b)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.4 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (138.1 mg, 1.0 mmol), iodo-
benzene (152.9 mg, 0.75 mmol), and 1b (97.6 mg, 0.50 mmol)
Scheme 5. Rational explanation for the regio- and stereoselectivity.
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Palladium-Catalyzed Highly Chemo-, Regio- and Stereoselective Synthesis of Eight- to Ten-Membered Lactones
in 4 mL of CH3CN afforded 2b (eluent: petroleum ether/
ethyl ether=10/1) as a liquid; yield: 112.5 mg (83%).
1H NMR (300 MHz, CDCl3): d=7.37–7.21 (m, 5H, Ar-H),
5.95 (t, J=8.0 Hz, 1H, =CH), 4.57 (t, J=11.3 Hz, 1H, one
proton from OCH2), 4.21–4.09 (m, 1H, one proton from
OCH2), 3.70 (dd, J1 =11.7 Hz, J2 =4.2 Hz, 1H, O2CCH), 3.45
[t, J=12.5 Hz, 1H, one proton from C=C(Ph)CH2], 2.90–
2.65 [m, 3H, one proton from C=C(Ph)CH2, one proton
from PhC=CCH2, and COCH(C)C], 2.30–2.17 (m, 1H, one
(%)=258 (M+, 4.18), 43 (100); HR-MS: m/z=258.1255,
calcd. for C16H18O3 (M+): 258.1256.
Synthesis of 3-Acetyl-3-ethyl-5-phenyl-5(E)-3,4,7,8-
tetrahydro-2H-oxocin-2-one (2e)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.2 mg, 0.050 mmol), K2CO3 (138.4 mg, 1.0 mmol), iodo-
benzene (255.6 mg, 1.25 mmol), and 1e (98.5 mg, 0.50 mmol)
in 4 mL of CH3CN afforded 2e (eluent: petroleum ether/
ethyl acetate=20/1) as a white solid; yield: 86.2 mg (63%);
mp 124–1258C (ethyl ether/petroleum ether). 1H NMR
(400 MHz, CDCl3): d=7.35–7.18 (m, 5H, Ar-H), 5.90 (t, J=
8.0 Hz, 1H, =CH), 4.63 (t, J=11.4 Hz, 1H, one proton from
OCH2), 4.12–3.97 (m, 1H, one proton from OCH2), 3.37 [d,
J=13.2 Hz, 1H, one proton from C=C(Ph)CH2], 2.88 [d, J=
13.6 Hz, 1H, one proton from C=C(Ph)CH2], 2.81–2.67 (m,
1H, one proton from PhC=CCH2), 2.29–2.17 (m, 1H, one
proton from PhC=CCH2), 2.12 (s, 3H, COCH3), 1.83–1.67
(m, 1H, one proton from O2CCCH2C), 1.39–1.25 (m, 1H,
one proton from O2CCCH2C), 0.48 (t, J=7.6 Hz, 3H,
CCH3); 13C NMR (100.5 MHz, CDCl3): d=204.4, 175.7,
144.5, 143.1, 128.3, 127.7, 127.1, 126.3, 69.9, 67.3, 32.8, 29.9,
26.7, 23.3, 7.75; IR (neat): n=1750, 1706, 1491, 1446, 1365,
1352, 1331, 1280, 1257, 1238, 1215, 1196, 1157, 1112, 1087,
1022 cmꢀ1; MS (70 eV, EI): m/z (%)=272 (M+, 1.56), 43
(100); anal. calcd. for C17H20O3 (%): C 74.97, H 7.40; found:
C 74.91, H 7.24.
proton from PhC=CCH2), 1.09 [t, J=6.5 Hz, 6H, CACHTUNTRGNEUNG(CH3)2];
13C NMR (75.4 MHz, CDCl3): d=206.8, 173.1, 142.7, 142.3,
128.4, 127.5, 126.5, 126.2, 68.7, 61.2, 40.3, 31.1, 29.9, 18.8,
17.9; IR (neat): n=2928, 1744, 1705, 1497, 1456, 1379, 1366,
1261, 1206, 1151, 1105, 1068, 1037, 1015 cmꢀ1; MS (70 eV,
EI): m/z (%)=272 (M+, 3.52), 43 (100); HR-MS: m/z=
272.1413, calcd. for C17H20O3 (M+): 272.1412.
Synthesis of 3-Benzoyl-5-phenyl-5(E)-3,4,7,8-tetra-
hydro-2H-oxocin-2-one (2c)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.4 mg, 0.050 mmol), K2CO3 (137.7 mg, 1.0 mmol), iodo-
benzene (152.0 mg, 0.75 mmol), and 1c (114.9 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2c (eluent: petrole-
um ether/ethyl ether=10/1) as an oil; yield: 120.5 mg
1
(79%). H NMR (300 MHz, CDCl3): d=8.00 (d, J=7.8 Hz,
2H, Ar-H), 7.53 (t, J=7.1 Hz, 1H, Ar-H), 7.40 (t, J=7.7 Hz,
2H, Ar-H), 7.36–7.20 (m, 5H, Ar-H), 6.01 (t, J=8.1 Hz, 1H,
=CH), 4.58 (t, J=11.4 Hz, 1H, one proton from OCH2),
4.36 (dd, J1 =11.6 Hz, J2 =4.1 Hz, 1H, O2CCH), 4.15–4.03
(m, 1H, one proton from OCH2), 3.75 [t, J=12.5 Hz, 1H,
one proton from C=C(Ph)CH2], 2.95–2.67 [m, 2H, one
proton from C=C(Ph)CH2 and one proton from PhC=
CCH2], 2.30–2.17 (m, 1H, one proton from PhC=CCH2);
13C NMR (75.4 MHz, CDCl3): d=192.1, 173.1, 142.6, 142.4,
135.7, 133.7, 128.7, 128.6, 128.5, 127.5, 126.5, 126.4, 68.7,
59.1, 31.4, 28.9; IR (neat): n=1743, 1684, 1597, 1580, 1491,
1448, 1365, 1326, 1279, 1212, 1194, 1145, 1103, 1076, 1045,
1014 cmꢀ1; MS (70 eV, EI): m/z (%)=306 (M+, 0.4), 105
(100); anal. calcd. for C20H18O3 (%): C 78.41, H 5.92; found:
C 78.41, H 5.97.
Synthesis of 3-Acetyl-3-allyl-5-phenyl-5(E)-3,4,7,8-
tetrahydro-2H-oxocin-2-one (2f)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.7 mg, 0.025 mmol), PPh3
(13.1 mg, 0.050 mmol), K2CO3 (138.7 mg, 1.0 mmol), iodo-
benzene (153.5 mg, 0.75 mmol), and 1f (104.8 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2f [eluent: petrole-
um ether (bp 30–608C)/ethyl acetate=20/1] as a white solid;
yield: 99.2 mg (69%); mp 77–788C (ethyl ether/petroleum
1
ether). H NMR (400 MHz, CDCl3): d=7.33–7.14 (m, 5H,
Ar-H), 5.90 (t, J=8.0 Hz, 1H, C=CH), 5.40–5.25 (m, 1H,
C=CHC), 4.87 (d, J=10.0 Hz, 1H, one proton from CH2 =
C), 4.65 (t, J=11.4 Hz, 1H, one proton from OCH2), 4.49
(d, J=17.2 Hz, 1H, one proton from CH2 =C), 4.10–4.00
(m, 1H, one proton from OCH2), 3.40 [d, J=13.2 Hz, 1H,
one proton from C=C(Ph)CH2], 2.83 [d, J=13.2 Hz, 1H,
one proton from C=C(Ph)CH2], 2.79–2.67 (m, 1H, one
proton from PhC=CCH2), 2.46 (dd, J1 =14.4 Hz, J2 =6.4 Hz,
1H, one proton from CH2C=C), 2.30–2.19 (m, 1H, one
proton from PhC=CCH2), 2.13 (s, 3H, CH3), 2.46 (dd, J1 =
14.8 Hz, J2 =8.2 Hz, 1H, one proton from CH2C=C);
13C NMR (100.5 MHz, CDCl3): d=203.7, 175.2, 144.6, 143.2,
131.2, 128.3, 128.0, 127.2, 126.6, 119.2, 69.4, 67.4, 35.1, 33.7,
30.0, 27.1; IR (neat): n=1748, 1709, 1490, 1465, 1443, 1366,
Synthesis of 3-Acetyl-3-methyl-5-phenyl-5(E)-3,4,7,8-
tetrahydro-2H-oxocin-2-one (2d)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.7 mg, 0.025 mmol), PPh3
(13.4 mg, 0.050 mmol), K2CO3 (138.5 mg, 1.0 mmol), iodo-
benzene (152.9 mg, 0.75 mmol), and 1d (90.1 mg, 0.50 mmol)
in 4 mL of CH3CN afforded 2d [eluent: petroleum ether
(b.p. 30–608C)/ethyl ether=10/1] as an oil; yield: 103.4 mg
1
(81%). H NMR (300 MHz, CDCl3): d=7.36–7.19 (m, 5H,
1272, 1254, 1231, 1187, 1160, 1129, 1110, 1069, 1012 cmꢀ1
;
Ar-H), 5.93 (t, J=8.0 Hz, 1H, =CH), 4.62 (t, J=11.4 Hz,
1H, one proton from OCH2), 4.12–3.98 (m, 1H, one proton
from OCH2), 3.52 [d, J=13.2 Hz, 1H, C=C(Ph)CH2], 2.82–
2.65 [m, 2H, one proton from C=C(Ph)CH2 and one proton
from PhC=CCH2], 2.30–2.19 (m, 1H, one proton from PhC=
CCH2), 2.16 (s, 3H, COCH3), 0.96 (s, 3H, CCH3); 13C NMR
(75.4 MHz, CDCl3): d=205.0, 176.0, 144.8, 143.0, 128.4,
127.5, 127.2, 126.3, 67.4, 65.5, 37.1, 30.0, 26.0, 18.5; IR
(neat): n=1748, 1708, 1488, 1451, 1380, 1361, 1319, 1295,
1266, 1215, 1162, 1101, 1088 cmꢀ1; MS (70 eV, EI): m/z
MS (70 eV, EI): m/z (%)=284 (M+, 1.44), 43 (100); anal.
calcd. for C18H20O3 (%): C 76.03, H 7.09; found: C 76.03, H
7.02.
Synthesis of 3-Benzoyl-5-p-tolyl-5(E)-3,4,7,8-tetra-
hydro-2H-oxocin-2-one (2g)
The reaction of Pd
ACHTUGNRTEN(NUGN OAc)2 (5.8 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (138.0 mg, 1.0 mmol), p-meth-
Adv. Synth. Catal. 2011, 353, 1763 – 1774
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1769

Baoqiang Wan et al.
FULL PAPERS
ylphenyl iodide (164.1 mg, 0.75 mmol), and 1c (115.0 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2g (eluent: petrole-
um ether/ethyl ether=10/1) as a white solid; yield: 120.1 mg
(75%); mp 110–1118C (ethyl ether/petroleum ether).
1H NMR (300 MHz, CDCl3): d=8.01 (d, J=7.5 Hz, 2H, Ar-
H), 7.55 (t, J=7.4 Hz, 1H, Ar-H), 7.43 (t, J=7.7 Hz, 2H,
Ar-H), 7.24 (d, J=7.5 Hz, 2H, Ar-H), 7.15 (d, J=8.1 Hz,
2H, Ar-H), 6.00 (t, J=8.1 Hz, 1H, =CH), 4.59 (t, J=
11.4 Hz, 1H, one proton from OCH2), 4.36 (dd, J1 =11.7 Hz,
J2 =4.2 Hz, 1H, O2CCH), 4.15–4.05 (m, 1H, one proton
(dd, J1 =11.7 Hz, J2 =4.2 Hz, 1H, O2CCH), 4.15–4.00 (m,
1H, one proton from OCH2), 3.73 [t, J=12.5 Hz, 1H, one
proton from C=C(Ar)CH2], 2.92–2.75 [m, 2H, one proton
from C=C(Ar)CH2 and one proton from ArC=CCH2], 2.35
(s, 3H, CH3), 2.28–2.14 (m, 1H, one proton from ArC=
CCH2); 13C NMR (75.4 MHz, CDCl3): d=192.0, 173.0,
142.6, 142.3, 137.9, 135.6, 133.6, 128.59, 128.55, 128.3, 128.2,
127.2, 126.1, 123.5, 68.6, 59.1, 31.3, 29.8, 21.3; IR (neat): n=
1742, 1684, 1597, 1580, 1486, 1448, 1363, 1325, 1282, 1249,
1212, 1182, 1141, 1103, 1047, 1017 cmꢀ1; MS (70 eV, EI): m/z
from OCH2), 3.73 [t, J=12.5 Hz, 1H, one proton from C= (%)=320 (M+, 0.74), 105 (100); anal. calcd. for C21H20O3
C(Ar)CH2], 2.95–2.77 [m, 2H, one proton from C= (%): C 78.73, H 6.29; found: C 78.94, H 6.64.
C(Ar)CH2 and one proton from ArC=CCH2], 2.35 (s, 3H,
CH3), 2.30–2.17 (m, 1H, one proton from ArC=CCH2);
Synthesis of 3-Benzoyl-5-(3,4-dimethylphenyl)-5(E)-
3,4,7,8-tetrahydro-2H-oxocin-2-one (2j)
13C NMR (75.4 MHz, CDCl3): d=192.1, 173.0, 142.4, 139.4,
137.3, 135.7, 133.7, 129.1, 128.7, 128.6, 126.3, 125.6, 68.8,
59.1, 31.3, 29.9, 21.0; IR (neat): n=1738, 1683, 1596, 1514,
1465, 1447, 1360, 1324, 1278, 1254, 1205, 1192, 1177, 1144,
1057, 1014 cmꢀ1; MS (70 eV, EI): m/z (%)=320 (M+, 2.57),
105 (100); anal. calcd. for C21H20O3 (%): C 78.73, H 6.29;
found: C 78.44, H 6.29.
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.7 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (138.5 mg, 1.0 mmol), 3,4-di-
methylphenyl iodide (174.5 mg, 0.75 mmol), and 1c
(113.9 mg, 0.50 mmol) in 4 mL of CH3CN afforded 2j
[eluent: petroleum ether (b.p. 30–608C)/ethyl ether=10/1]
as an oil; yield: 119.2 mg (72%). 1H NMR (300 MHz,
CDCl3): d=8.01 (d, J=7.8 Hz, 2H, Ar-H), 7.54 (t, J=
7.2 Hz, 1H, Ar-H), 7.42 (t, J=7.7 Hz, 2H, Ar-H), 7.16–7.04
(m, 3H, Ar-H), 6.00 (t, J=8.0 Hz, 1H, =CH), 4.58 (t, J=
11.4 Hz, 1H, one proton from OCH2), 4.36 (dd, J1 =11.6 Hz,
J2 =4.1 Hz, 1H, O2CCH), 4.15–4.05 (m, 1H, one proton
from OCH2), 3.72 [t, J=12.3 Hz, 1H, one proton from C=
C(Ar)CH2], 2.95–2.78 [m, 2H, one proton from C=
C(Ar)CH2 and one proton from ArC=CCH2], 2.35–2.17 (m,
7H, one proton from ArC=CCH2 and 2ꢂAr-CH3);
13C NMR (75.4 MHz, CDCl3): d=192.3, 173.1, 142.5, 139.9,
136.6, 136.0, 135.8, 133.7, 129.7, 128.7, 127.8, 125.5, 123.9,
68.9, 59.2, 31.4, 29.9, 19.8, 19.3; IR (neat): n=1743, 1685,
1598, 1580, 1501, 1448, 1362, 1326, 1278, 1248, 1213, 1195,
1176, 1143, 1127, 1100, 1048, 1018 cmꢀ1; MS (70 eV, EI); m/
z (%)=334 (M+, 3.22), 105 (100); HR-MS: m/z=334.1567,
calcd. for C22H22O3 (M+): 334.1569.
Synthesis of 3-Benzoyl-5-(4-methoxyphenyl)-5(E)-
3,4,7,8-tetrahydro-2H-oxocin-2-one (2h)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.4 mg, 0.050 mmol), K2CO3 (138.5 mg, 1.0 mmol), p-me-
thoxyphenyl iodide (176.1 mg, 0.75 mmol), and 1c (115.3 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2h [eluent: petrole-
um ether (b.p. 30–608C)/ethyl ether=10/1] as a white solid;
yield 116.8 mg (69%); mp 132–1338C (ethyl ether/petroleum
1
ether). H NMR (300 MHz, CDCl3): d=8.00 (d, J=7.8 Hz,
2H, Ar-H), 7.54 (t, J=7.4 Hz, 1H, Ar-H), 7.42 (t, J=7.5 Hz,
2H, Ar-H), 7.28 (d, J=8.7 Hz, 2H, Ar-H), 6.87 (d, J=
8.7 Hz, 2H, Ar-H), 5.96 (t, J=8.0 Hz, 1H, =CH), 4.58 (t, J=
11.4 Hz, 1H, one proton from OCH2), 4.35 (dd, J1 =11.6 Hz,
J2 =4.1 Hz, 1H, O2CCH), 4.15–4.05 (m, 1H, one proton
from OCH2), 3.80 (s, 3H, OMe), 3.72 [t, J=12.3 Hz, 1H,
one proton from C=C(Ar)CH2], 2.95–2.77 [m, 2H, one
proton from C=C(Ar)CH2 and one proton from ArC=
CCH2], 2.30–2.15 (m, 1H, ArC=CCH2); 13C NMR
(75.4 MHz, CDCl3): d=192.2, 173.1, 159.2, 142.0, 135.7,
134.7, 133.7, 128.70, 128.65, 127.6, 125.0, 113.8, 69.0, 59.2,
55.2, 31.3, 29.0; IR (neat): n=1742, 1684, 1600, 1575, 1513,
1462, 1426, 1330, 1293, 1275, 1238, 1205, 1190, 1139, 1057,
1028, 1012 cmꢀ1; MS (70 eV, EI): m/z (%)=336 (M+, 10.39),
77 (100); anal. calcd. for C21H20O4 (%): C 74.98, H 5.99;
found: C 75.02, H 6.04.
Synthesis of 3-Benzoyl-5-(2,3 dihydrobenzo[b]ACTHNUGTRNEUNG[1,4]-
dioxin-6-yl)-5(E)-3,4,7,8-tetrahydro-2H-oxocin-2-one
(2k)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.4 mg, 0.050 mmol), K2CO3 (138.9 mg, 1.0 mmol), 6-iodo-
1,4-benzodioxane (196.5 mg, 0.75 mmol), and 1c (116.0 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2k [eluent: petrole-
um ether (bp 30–608C)/ethyl ether=10/1] as a white solid;
yield: 121.3 mg (66%); mp 142–1438C (ethyl ether/petrole-
um ether). 1H NMR (300 MHz, CDCl3): d=8.02 (d, J=
7.8 Hz, 2H, Ar-H), 7.55 (t, J=7.4 Hz, 1H, Ar-H), 7.43 (t,
J=7.4 Hz, 2H, Ar-H), 6.93–6.77 (m, 3H, Ar-H), 5.98 (t, J=
8.1 Hz, 1H, =CH), 4.56 (t, J=11.6 Hz, 1H, one proton from
OCH2), 4.37 (dd, J1 =11.6 Hz, J2 =4.1 Hz, 1H, O2CCH), 4.25
(s, 4H, OCH2CH2O), 4.15–4.02 (m, 1H, one proton from
OCH2), 3.70 [t, J=12.5 Hz, 1H, one proton from C=
C(Ar)CH2], 2.93–2.70 [m, 2H, one proton from C=
C(Ar)CH2 and one proton from ArC=CCH2], 2.29–2.15 (m,
1H, one proton from ArC=CCH2); 13C NMR (75.4 MHz,
CDCl3): d=192.2, 173.0, 143.3, 143.2, 141.7, 135.8, 135.7,
Synthesis of 3-Benzoyl-5-(m-tolyl)-5(E)-3,4,7,8-tetra-
hydro-2H-oxocin-2-one (2i)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (138.4 mg, 1.0 mmol), m-
methylphenyl iodide (163.0 mg, 0.75 mmol), and 1c
(115.6 mg, 0.50 mmol) in 4 mL of CH3CN afforded 2i
[eluent: petroleum ether (bp 30–608C)/ethyl ether=10/1] as
1
an oil; yield: 124.8 mg (78%). H NMR (300 MHz, CDCl3):
d=8.00 (d, J=7.8 Hz, 2H, Ar-H), 7.52 (t, J=7.4 Hz, 1H,
Ar-H), 7.40 (t, J=7.7 Hz, 2H, Ar-H), 7.22 (t, J=7.4 Hz, 1H,
Ar-H), 7.17–7.05 (m, 3H, Ar-H), 5.99 (t, J=8.0 Hz, 1H, = 133.7, 128.71, 128.69, 125.2, 119.5, 117.2, 115.3, 68.9, 64.4,
CH), 4.57 (t, J=11.4 Hz, 1H, one proton from OCH2), 4.35 64.3, 59.2, 31.2, 29.9; IR (neat): n=1742, 1688, 1596, 1579,
1770
asc.wiley-vch.de
ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2011, 353, 1763 – 1774

Palladium-Catalyzed Highly Chemo-, Regio- and Stereoselective Synthesis of Eight- to Ten-Membered Lactones
1510, 1452, 1429, 1360, 1329, 1300, 1249, 1206, 1131, 1101,
1068, 1051, 1014 cmꢀ1; MS (70 eV, EI): m/z (%)=364 (M+,
8.38), 77 (100); anal. calcd. for C22H20O5 (%): C 72.51, H
5.53; found: C 72.48, H 5.30.
thiophene (156.5 mg, 0.75 mmol), and 1c (114.5 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2n [eluent: petrole-
um ether (bp 30–608C)/ethyl ether=10/1] as a white solid;
yield: 108.1 mg (70%); mp 120–1228C (ethyl ether/petrole-
um ether). 1H NMR (300 MHz, CDCl3): d=8.04 (d, J=
7.8 Hz, 2H, Ar-H), 7.56 (t, J=7.4 Hz, 1H, Ar-H), 7.44 (t,
J=7.7 Hz, 2H, Ar-H), 7.35–7.23 (m, 1H, Ar-H), 7.22–7.12
(m, 2H, Ar-H), 6.22 (t, J=8.1 Hz, 1H, =CH), 4.57 (t, J=
11.4 Hz, 1H, one proton from OCH2), 4.48 (dd, J1 =11.7 Hz,
J2 =4.2 Hz, 1H, O2CCH), 4.20–4.05 (m, 1H, one proton
from OCH2), 3.71 [t, J=12.5 Hz, 1H, one proton from C=
C(Ar)CH2], 2.95–2.75 [m, 2H, one proton from C=
C(Ar)CH2 and one proton from ArC=CCH2], 2.30–2.15 (m,
1H, one proton from ArC=CCH2); 13C NMR (75.4 MHz,
CDCl3): d=192.2, 172.8, 142.8, 136.9, 135.7, 133.8, 128.75,
128.67, 126.1, 125.5, 124.9, 120.2, 69.1, 59.2, 30.7, 29.7; IR
(neat): n=1742, 1685, 1598, 1579, 1461, 1448, 1424, 1358,
1324, 1286, 1268, 1249, 1204, 1174, 1133, 1102, 1040,
1013 cmꢀ1; MS (70 eV, EI): m/z (%)=312 (M+, 2.01), 77
(100); anal. calcd. for C18H16O3S (%): C 69.21, H 5.16, S
10.26; found: C 69.49, H 5.02, S 10.25.
Synthesis of 3-Benzoyl-5-(4-ethoxycarbonylphenyl)-
5(E)-3,4,7,8-tetrahydro-2H-oxocin-2-one (2l)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.7 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (138.7 mg, 1.0 mmol), ethyl 4-
iodobenzoate (206.9 mg, 0.75 mmol), and 1c (115.9 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2l [eluent: petrole-
um ether (bp 30–608C)/dichloromethane=1/2] as a white
solid; yield: 111.3 mg (58%); mp 123–1248C (ethyl ether/pe-
troleum ether). 1H NMR (300 MHz, CDCl3): d=8.07–7.92
(m, 4H, Ar-H), 7.56 (t, J=7.4 Hz, 1H, Ar-H), 7.48–7.32 (m,
4H, Ar-H), 6.12 (t, J=8.0 Hz, 1H, =CH), 4.60 (t, J=
11.3 Hz, 1H, one proton from OCH2CC), 4.45–4.25 (m, 3H,
p-Ar-CO2CH2 and O2CCH), 4.20–4.05 (m, 1H, one proton
from OCH2CC), 3.78 [t, J=12.5 Hz, 1H, one proton from
C=C(Ar)CH2], 2.95–2.75 [m, 2H, one proton from C=
C(Ar)CH2 and one proton from ArC=CCH2], 2.35–2.12 (m,
1H, one proton from ArC=CCH2), 1.39 (t, J=7.2 Hz, 3H,
CH3); 13C NMR (75.4 MHz, CDCl3): d=191.9, 173.0, 166.3,
146.8, 142.0, 135.7, 133.8, 129.8, 129.6, 128.8, 128.7, 128.2,
126.5, 68.4, 60.9, 59.1, 31.2, 30.0, 14.3; IR (neat): n=1743,
1716, 1687, 1607, 1597, 1459, 1449, 1406, 1365, 1316, 1276,
1255, 1207, 1193, 1179, 1144, 1105, 1013 cmꢀ1; MS (70 ev,
EI) m/z (%): 378 (M+, 0.16), 105 (100); anal. calcd. for
C23H22O5 (%): C 73.00, H 5.86; found: C 72.98, H 6.08.
Synthesis of 3-Benzoyl-5-[(E)-hex-1-enyl]-5(E)-
3,4,7,8-tetrahydro-2H-oxocin-2-one (2o)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.6 mg, 0.025 mmol), PPh3
(13.2 mg, 0.050 mmol), K2CO3 (138.7 mg, 1.0 mmol), (E)-1-
iodohex-1-ene (157.3 mg, 0.75 mmol), and 1c (114.9 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2o [eluent: petrole-
um ether (b.p. 30–608C)/ethyl ether=15/1] as a white solid;
yield: 92.0 mg (59%); mp 70–718C (ethyl ether/petroleum
1
Synthesis of 3-Benzoyl-5-(4-bromophenyl)-5(E)-
3,4,7,8-tetrahydro-2H-oxocin-2-one (2m)
ether). H NMR (300 MHz, CDCl3): d=8.07 (d, J=8.1 Hz,
2H, Ar-H), 7.58 (t, J=7.4 Hz, 1H, Ar-H), 7.47 (t, J=7.5 Hz,
2H, Ar-H), 6.04 (d, J=15.9 Hz, 1H, C=CCH=C), 5.75 [t,
J=8.1 Hz, 1H, CH=C(C)C=C], 5.71–5.58 (m, 1H, C=CC=
CHC), 4.53 (t, J=11.4 Hz, 1H, one proton from OCH2),
4.44 (dd, J1 =11.4 Hz, J2 =3.9 Hz, 1H, O2CCH), 4.15–4.00
(m, 1H, one proton from OCH2), 3.42 [t, J=12.6 Hz, 1H,
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.4 mg, 0.025 mmol), PPh3
(13.5 mg, 0.050 mmol), K2CO3 (137.4 mg, 1.0 mmol), 1-
bromo-4-iodobenzene (211.7 mg, 0.75 mmol), and 1c
(113.8 mg, 0.50 mmol) in 4 mL of CH3CN afforded 2m
[eluent: petroleum ether (bp 30–608C)/ethyl ether=15/1] as
a solid; yield: 120.8 mg (63%); mp 136–1378C (ethyl ether/
one proton from C=C
ACHTUNGERTN(NUNG C=C)CH2], 2.87–2.63 [m, 2H, one
proton from C=C(C=C)CH2 and one proton from CH2C=
AHCTUNGTRENNUNG
1
petroleum ether). H NMR (300 MHz, CDCl3): d=8.01 (d,
CC=C], 2.25–2.01 (m, 3H, CH2CC, and one proton from
CH2C=CC=C), 1.47–1.20 (m, 4H, CCH2CH2C), 0.90 (t, J=
6.8 Hz, 3H, CH3); 13C NMR (75.4 MHz, CDCl3): d=192.4,
172.8, 140.2, 135.8, 133.7, 132.5, 129.5, 128.74, 128.65, 127.3,
69.8, 58.9, 32.4, 31.5, 29.6, 26.8, 22.2, 13.9; IR (neat): n=
1744, 1686, 1597, 1581, 1453, 1422, 1380, 1353, 1325, 1284,
J=7.5 Hz, 2H, Ar-H), 7.56 (t, J=7.4 Hz, 1H, Ar-H), 7.52–
7.37 (m, 4H, Ar-H), 7.21 (d, J=8.7 Hz, 2H, Ar-H), 6.02 (t,
J=8.0 Hz, 1H, =CH), 4.59 (t, J=11.4 Hz, 1H, one proton
from OCH2), 4.33 (dd, J1 =11.6 Hz, J2 =4.4 Hz, 1H,
O2CCH), 4.15–4.05 (m, 1H, one proton from OCH2), 3.75 [t,
J=12.5 Hz, 1H, one proton from C=C(Ar)CH2], 2.95–2.75
[m, 2H, one proton from C=C(Ar)CH2 and one proton
from ArC=CCH2], 2.32–2.13 (m, 1H, one proton from
ArC=CCH2); 13C NMR (75.4 MHz, CDCl3): d=191.9, 173.0,
141.7, 141.3, 135.6, 133.8, 131.6, 128.8, 128.6, 128.2, 127.1,
121.6, 68.5, 59.0, 31.3, 29.9; IR (neat): n=1748, 1681, 1596,
1580, 1487, 1446, 1424, 1394, 1364, 1324, 1310, 1275, 1253,
1208, 1194, 1177, 1145, 1108, 1074, 1057, 1010 cmꢀ1; MS (70
1264, 1248, 1206, 1188, 1173, 1140, 1120, 1056, 1010 cmꢀ1
;
MS (70 eV, EI): m/z (%)=312 (M+, 0.18), 105 (100); anal.
calcd. for C20H24O3 (%): C 76.89, H 7.74; found: C 77.16, H
7.99.
Synthesis of 3-Benzoyl-5-styryl-5(E)-3,4,7,8-tetra-
hydro-2H-oxocin-2-one (2p)
eV, EI): m/z (%)=386 [MACTHNUGTRENNUG ACHUTNGTRENNGUN
(81Br)+, 0.53], 384 [M(79Br)+,
0.56], 105 (100); anal. calcd. for C20H17BrO3 (%): C 62.35, H
4.45; found: C 62.15, H 4.61.
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.7 mg, 0.025 mmol), PPh3
(13.3 mg, 0.050 mmol), K2CO3 (139.0 mg, 1.0 mmol), (E)-(2-
iodovinyl)benzene (173.3 mg, 0.75 mmol), and 1c (115.0 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2p [eluent: petrole-
um ether (b.p. 30–608C)/ethyl ether=15/1] as a white solid;
yield: 95.8 mg (58%); mp 116–1178C (ethyl ether/petroleum
Synthesis of 3-Benzoyl-5-(3-thienyl)-5(E)-3,4,7,8-
tetrahydro-2H-oxocin-2-one (2n)
1
The reaction of Pd
N
ether); H NMR (300 MHz, CDCl3): d=8.09 (d, J=8.1 Hz,
(13.3 mg, 0.050 mmol), K2CO3 (138.1 mg, 1.0 mmol), 3-iodo-
2H, Ar-H), 7.58 (t, J=7.1 Hz, 1H, Ar-H), 7.52–7.37 (m, 4H,
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Baoqiang Wan et al.
FULL PAPERS
Ar-H), 7.31 (t, J=7.4 Hz, 2H, Ar-H), 7.22 (t, J=7.2 Hz, 1H,
Ar-H), 6.78 [d, J=16.2 Hz, 1H, C=CCH=C(Ph)], 6.51 [d,
J=16.2 Hz, 1H, C=CC=CCH(Ph)], 6.01 [t, J=8.1 Hz, 1H,
CH=CC=C(Ph)], 4.62–4.45 (m, 2H, one proton from OCH2
and O2CCH), 4.20–4.05 (m, 1H, one proton from OCH2),
(Ar)C=CCH2 and COCH3], 2.06–1.85 (m, 2H, CCH2C);
13C NMR (75.4 MHz, CDCl3): d=201.7, 170.7, 158.8, 136.0,
134.7, 130.5, 127.7, 113.7, 63.3, 58.3, 55.2, 30.0, 28.8, 26.9,
23.2; IR (neat): n=1714, 1607, 1573, 1510, 1462, 1358, 1291,
1244, 1218, 1178, 1150, 1064, 1030 cmꢀ1; MS (70 eV, EI): m/z
(%)=288 (M+, 27.16), 43 (100); HR-MS: m/z=288.1361,
calcd. for C17H20O4 (M+): 288.1362.
3.54 [t, J=12.8 Hz, 1H, one proton from C=C
ACHTUNGTERNN(UNG C=C)CH2],
2.95–2.75 [m, 2H, one proton from C=C(C=C)CH2 and one
AHCTUNGTRENNUNG
proton from (C=C)C=CCH2], 2.20 [dd, J1 =13.8 Hz, J2 =
8.4 Hz, 1H, one proton from (C=C)C=CCH2]; 13C NMR
(75.4 MHz, CDCl3): d=192.2, 172.7, 140.3, 137.0, 135.8,
133.8, 131.4, 130.7, 128.8, 128.7, 128.6, 127.5, 127.2, 126.4,
69.5, 58.9, 29.9, 26.7; IR (neat): n=1742, 1684, 1597, 1580,
1495, 1448, 1356, 1325, 1275, 1249, 1212, 1182, 1129, 1075,
1015 cmꢀ1; MS (70 eV, EI): m/z (%)=332 (M+, 6.13), 105
(100); anal. calcd. for C22H20O3 (%): C 79.50, H 6.06; found:
C 79.56, H 6.27.
Synthesis of 3-Acetyl-5-(4-nitrophenyl)-5(E)-3,4,8,9-
tetrahydrooxonin-2(3H)-one (2s)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.4 mg, 0.025 mmol), PPh3
(13.1 mg, 0.05 mmol), K2CO3 (138.0 mg, 1.0 mmol), 1-iodo-
4-nitrobenzene (186.6 mg, 0.75 mmol), and 1g (91.5 mg,
0.5 mmol) in 4 mL of CH3CN afforded 2s (eluent: petroleum
ether/ethyl ether=5/1) as a yellow solid; yield: 112.8 mg
(74%); mp 115–1168C (ethyl ether/petroleum ether).
1H NMR (300 MHz, CDCl3): d=8.15 (d, J=8.7 Hz, 2H, Ar-
H), 7.43 (d, J=8.7 Hz, 2H, Ar-H), 5.92 (dd, J1 =11.1 Hz,
J2 =6.6 Hz, 1H, =CH), 4.57–4.46 (m, 1H, one proton from
OCH2), 4.31–4.17 (m, 1H, one proton from OCH2), 3.37–
3.15 [m, 2H, O2CCH and one proton from C=C(Ar)CH2],
2.86 [dd, J1 =13.2 Hz, J2 =3.3 Hz, 1H, one proton from C=
C(Ar)CH2], 2.48–2.33 [m, 1H, one proton from (Ar)C=
CCH2], 2.33–2.17 [m, 4H, one proton from (Ar)C=CCH2
and CH3], 2.11–1.88 (m, 2H, CCH2C); 13C NMR (75.4 MHz,
CDCl3): d=201.0, 170.4, 149.0, 146.8, 135.3, 135.2, 127.4,
123.7, 63.3, 57.9, 29.5, 28.8, 26.8, 23.5; IR (neat): n=1710,
1592, 1511, 1460, 1441, 1343, 1317, 1284, 1263, 1209, 1159,
1149, 1100, 1060, 1025 cmꢀ1; MS (70 eV, EI): m/z (%)=303
(M+, 3.07), 43 (100); anal. calcd. for C16H17NO5 (%): C
63.36, H 5.65, N 4.62; found: C 63.33, H 5.64, N 4.61.
Synthesis of 3-Acetyl-5-phenyl-5(E)-3,4,8,9-tetra-
hydrooxonin-2(3H)-one (2q)
To a three-necked flask were added PdACTHNUTRGENUG(N OAc)2 (67.3 mg,
0.3 mmol), PPh3 (158.0 mg, 0.6 mmol), K2CO3 (1.6581 g,
12.0 mmol), CH3CN (28 mL), iodobenzene (1.8366 g,
9.0 mmol), CH3CN (1 mL), 1g (1.0947 g, 6.0 mmol), and
CH3CN (1 mL) sequentially under argon. The mixture was
stirred at 858C with a preheated oil bath and monitored by
TLC. Upon completion, the resulting mixture was filtered to
remove the solid and the filtrate was concentrated. The resi-
due was purified by chromatography on silica gel to afford
2q (eluent: petroleum ether/ethyl acetate=10/1) as a liquid;
yield: 1.2690 g (82%). 1H NMR (300 MHz, CDCl3): d=
7.39–7.17 (m, 5H, Ar-H), 5.77 (dd, J1 =11.1 Hz, J2 =6.6 Hz,
1H, =CH), 4.60–4.46 (m, 1H, one proton from OCH2),
4.25–4.12 (m, 1H, one proton from OCH2), 3.33–3.17 [m,
2H, O2CCH, and one proton from C=C(Ph)CH2], 2.86 [dd,
J1 =19.7 Hz, J2 =11.1 Hz, 1H, one proton from C=
C(Ph)CH2], 2.47–2.27 [m, 1H, one proton from (Ph)C=
CCH2], 2.27–2.12 [m, 4H, one proton from (Ph)C=CCH2
and CH3], 2.06–1.85 (m, 2H, CCH2C); 13C NMR (75.4 MHz,
CDCl3): d=201.6, 170.7, 142.4, 136.6, 131.9, 128.3, 127.1,
126.7, 63.3, 58.2, 30.0, 28.8, 26.9, 23.3; IR (neat): n=1714,
1598, 1492, 1462, 1445, 1377, 1358, 1275, 1218, 1150, 1064,
1042, 1028 cmꢀ1; MS (70 eV, EI): m/z (%)=258 (M+, 16.80),
43 (100); HR-MS: m/z=258.1258, calcd. for C16H18O3 (M+):
258.1256.
Synthesis of 3-Acetyl-5-phenyl-5(E)-3,4,7,8,9,10-
hexahydro-2H-oxecin-2-one (2t)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.7 mg, 0.025 mmol), PPh3
(13.1 mg, 0.05 mmol), K2CO3 (137.4 mg, 1.0 mmol), iodoben-
zene (152.2 mg, 0.75 mmol), and 1h (97.8 mg, 0.5 mmol) in
4 mL of CH3CN afforded 2t [eluent: petroleum ether (b.p.
30–608C)/ethyl acetate=15/1] as a solid; yield: 96.4 mg
(71%); m.p.: 100–1018C (ethyl ether/petroleum ether).
1H NMR (300 MHz, CDCl3): d=7.40–7.17 (m, 5H, Ar-H),
5.56 (dd, J1 =12.3 Hz, J2 =3.9 Hz, 1H, =CH), 4.93–4.81 (m,
1H, one proton from OCH2), 3.79 (t, J=11.4 Hz, 1H, one
proton from OCH2), 3.40–3.25 [m, 2H, O2CCH and one
proton from C=C(Ph)CH2], 2.93–2.64 (m, 2H), 2.28–2.12
(m, 4H), 2.12–1.85 (m, 1H), 1.85–1.72 (m, 2H), 1.59–1.45
(m, 1H); 13C NMR (75.4 MHz, CDCl3): d=202.0, 168.1,
142.1, 136.9, 131.6, 128.4, 127.2, 126.7, 67.2, 59.4, 28.5, 27.8,
27.4, 27.2, 25.0; IR (neat): n=1712, 1573, 1489, 1456, 1442,
1384, 1354, 1315, 1292, 1257, 1220, 1206, 1178, 1149, 1049,
1028 cmꢀ1; MS (70 eV, EI): m/z (%)=272 (M+, 4.88), 43
(100); anal. calcd. for C17H20O3 (%): C 74.97, H 7.40; found:
C 74.65, H 7.29.
Synthesis of 3-Acetyl-5-(4-methoxyphenyl)-5(E)-
3,4,8,9-tetrahydrooxonin-2(3H)-one (2r)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.8 mg, 0.025 mmol), PPh3
(13.3 mg, 0.05 mmol), K2CO3 (138.5 mg, 1.0 mmol), p-me-
thoxyphenyl iodide (174.6 mg, 0.75 mmol), and 1g (92.1 mg,
0.5 mmol) in 4 mL of CH3CN afforded 2r (eluent: petroleum
ether/ethyl acetate=10/1) as
a liquid; yield: 114.4 mg
1
(78%). H NMR (300 MHz, CDCl3): d=7.21 (d, J=8.7 Hz,
2H, Ar-H), 6.84 (d, J=8.7 Hz, 2H, Ar-H), 5.71 (dd, J1 =
11.1 Hz, J2 =6.3 Hz, 1H, =CH), 4.58–4.46 (m, 1H, one
proton from OCH2), 4.25–4.12 (m, 1H, one proton from
OCH2), 3.79 (s, 3H, OCH3), 3.30–3.16 [m, 2H, O2CCH and
one proton from C=C(Ar)CH2], 2.88–2.75 [m, 1H, one
proton from C=C(Ar)CH2], 2.46–2.27 [m, 1H, one proton
from (Ar)C=CCH2], 2.27–2.12 [m, 4H, one proton from
Synthesis of 3-Acetyl-5-(4-bromophenyl)-5(E)-
3,4,7,8,9,10-hexahydro-2H-oxecin-2-one (2u)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.6 mg, 0.025 mmol), PPh3
(13.1 mg, 0.05 mmol), K2CO3 (138.1 mg, 1.0 mmol), 1-
bromo-4-iodobenzene (212.6 mg, 0.75 mmol), and 1h
(98.9 mg, 0.5 mmol) in 4 mL of CH3CN afforded 2u (eluent:
1772
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Adv. Synth. Catal. 2011, 353, 1763 – 1774

Palladium-Catalyzed Highly Chemo-, Regio- and Stereoselective Synthesis of Eight- to Ten-Membered Lactones
petroleum ether/dichloromethane=1/1!2/3) as a yellow
solid; yield: 122.4 mg (69%); mp 95–968C (ethyl ether/pe-
troleum ether); H NMR (300 MHz, CDCl3): d=7.40 (d, J=
129.8, 128.4, 128.3, 128.1, 127.3, 127.0, 126.7, 70.6, 67.0, 38.5,
36.5, 29.9, 28.8; IR (neat): n=1746, 1709, 1600, 1491, 1459,
1437, 1360, 1321, 1298, 1262, 1227, 1210, 1172, 1154, 1111,
1067, 1050, 1006 cmꢀ1; MS (70 eV, EI): m/z (%)=334 (M+,
1.34), 43 (100); anal. calcd. for C22H22O3 (%): C 79.02, H
6.63; found: C 79.09, H 6.64.
1
8.4 Hz , 2H, Ar-H), 7.12 (d, J=8.4 Hz, 2H, Ar-H), 5.54 (dd,
J1 =12.3 Hz, J2 =3.9 Hz, 1H, =CH), 4.90–4.76 (m, 1H, one
proton from OCH2), 3.77 (t, J=11.1 Hz, 1H, one proton
from OCH2), 3.35–3.20 [m, 2H, O2CCH and one proton
from C=C(Ar)CH2], 2.87–2.55 (m, 2H), 2.26–2.10 (m, 4H),
1.99–1.68 (m, 3H), 1.57–1.43 (m, 1H); 13C NMR (75.4 MHz,
CDCl3): d=201.5, 167.9, 140.9, 135.8, 132.2, 131.5, 128.3,
121.0, 67.2, 59.2, 28.5, 27.5, 27.4, 27.1, 24.9; IR (neat): n=
1736, 1705, 1482, 1455, 1432, 1392, 1362, 1315, 1291, 1264,
Synthesis of 3-acetyl-5-(4-nitrophenyl)-5(E)-3,4,7,8-
tetrahydro-2H-oxocin-2-one (2x)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.6 mg, 0.025 mmol), PPh3
(13.0 mg, 0.050 mmol), K2CO3 (138.7 mg, 1.0 mmol), 1-iodo-
4-nitrobenzene (186.5 mg, 0.75 mmol), and 1k (92.1 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2x [eluent: petrole-
um ether/ethyl acetate=9/1] as a solid; yield: 99.6 mg
(65%); mp 144–1458C (CH2Cl2/petroleum ether). The major
1223, 1204, 1182, 1154, 1100, 1071, 1046, 1020, 1009 cmꢀ1
MS (70 eV, EI): m/z=(%): 353 [M
(81Br)+, 0.87], 351
[M
(79Br)+, 0.79], 43 (100); anal. calcd. for C17H19BrO3 (%):
;
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
C 58.13, H 5.45; found: C 58.13, H 5.17.
1
isomer: H NMR (300 MHz, CDCl3): d=8.15 (d, J=8.7 Hz,
2H, Ar-H), 7.41 (d, J=8.7 Hz, 2H, Ar-H), 5.72 (d, J=
7.2 Hz, 1H, C=CH), 4.29 (t, J=11.0 Hz, 1H, one proton
from OCH2), 4.02 (dd, J1 =10.7 Hz, J2 =4.4 Hz, 1H), 3.51
(dd, J1 =11.9 Hz, J2 =4.1 Hz, 1H), 3.38 (t, J=12.5 Hz, 1H),
3.07–2.91 (m, 1H, CHCH3), 2.79 (dd, J1 =13.2 Hz, J2 =
3.9 Hz, 1H), 2.22 (s, 3H, COCH3), 1.06 (d, J=6.9 Hz, 3H,
CCH3); 13C NMR (75.4 MHz, CDCl3): d=200.1, 172.5,
148.7, 147.1, 139.6, 137.5, 127.3, 123.7, 72.9, 63.8, 35.2, 31.3,
28.9, 15.8; IR (neat) n=2962, 2926, 1754, 1705, 1592, 1511,
1456, 1342, 1259, 1207, 1175, 1143, 1112, 1072, 1038,
1000 cmꢀ1; MS (70 eV, EI): m/z (%)=303 (M+, 1.63), 43
(100); anal. calcd. for C16H17NO5 (%): C 63.36, H 5.65, N
4.62; found: C 63.36, H 5.62, N 4.41.
Synthesis of 3-Acetyl-3-propyl-5-phenyl-5(E)-3,4,7,8-
tetrahydro-2H-oxocin-2-one (2v)
The reaction of PdACHTNUTRGNEUNG(OAc)2 (5.5 mg, 0.025 mmol), PPh3
(13.2 mg, 0.050 mmol), K2CO3 (138.5 mg, 1.0 mmol), iodo-
benzene (255.1 mg, 1.25 mmol), and 1i (106.0 mg,
0.50 mmol) in 4 mL of CH3CN afforded 2v [eluent: petrole-
um ether/ethyl ether=10/1] as a white solid; yield: 96.1 mg
(67%); mp 111–1128C (ethyl ether/petroleum ether).
1H NMR (300 MHz, CDCl3): d=7.33–7.19 (m, 5H, Ar-H),
5.91 (t, J=7.8 Hz, 1H, C=CH), 4.62 (t, J=11.1 Hz, 1H, one
proton from OCH2), 4.11–4.00 (m, 1H, one proton from
OCH2), 3.37 [d, J=13.2 Hz, 1H, one proton from C=
C(Ph)CH2], 2.90 [d, J=13.2 Hz, 1H, one proton from C=
C(Ph)CH2], 2.81–2.65 (m, 1H, one proton from PhC=
CCH2), 2.29–2.17 (m, 1H, one proton from PhC=CCH2),
2.11 (s, 3H, COCH3), 1.73–1.59 (m, 1H, one proton from
O2CCCH2C), 1.28–1.15 (m, 2H), 1.00–0.69 (m, 2H, one
proton from O2CCCCH2), 0.44 (t, J=7.2 Hz, 3H, CCH3);
13C NMR (75.4 MHz, CDCl3): d=204.3, 175.7, 144.5, 143.2,
128.3, 127.4, 127.1, 126.3, 69.5, 67.4, 33.0, 32.3, 29.9, 26.6,
16.7, 13.8; IR (neat): n=1749, 1709, 1598, 1490, 1462, 1442,
1360, 1320, 1301, 1268, 1248, 1193, 1159, 1106, 1078, 1051,
1032, 1008 cmꢀ1; MS (70 eV, EI): m/z (%)=286 (M+, 1.57),
43 (100); anal. calcd. for C18H22O3 (%): C 75.50, H 7.74;
found: C 75.44, H 7.82.
Acknowledgements
Financial support from the State Key Basic Research & De-
velopment Program (2011CB808700) and National Natural
Science Foundation of China (20732005) are greatly appreci-
ated. We thank Mr. B. Lꢀ in this group for reproducing the
preparation of 2d in Table 3, 2i and 2o in Table 4, and E-2u
in Scheme 3.
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Synthesis of 3-Acetyl-3-benzyl-5-phenyl-5(E)-3,4,7,8-
tetrahydro-2H-oxocin-2-one (2w)
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benzene (155.0 mg, 0.75 mmol), and 1j (128.8 mg,
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3.41 (d, J=12.9 Hz, 1H), 3.17 (d, J=14.1 Hz, 1H), 2.89 (d,
J=13.2 Hz, 1H), 2.78–2.62 (m, 1H, one proton from PhC=
CCH2), 2.57 (d, J=14.4 Hz, 1H), 2.35–2.22 (m, 1H, one
proton from PhC=CCH2), 1.93 (s, 3H, COCH3); 13C NMR
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ꢁ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1773

Baoqiang Wan et al.
FULL PAPERS
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R1=0.1140, wR2=0.1688, a=12.2236(10) ꢃ, b=
16.4269(13) ꢃ, c=18.2484(15) ꢃ, a=758, b=708, g=
908, V=3328.2(5) ꢃ3, T=173(2) K, Z=2, reflections
collected/unique 38333/11633 (Rint =0.0618), number of
observations [> 2s(I)] 7873, parameters: 865. Supple-
mentary crystallographic data have been deposited at
the Cambridge Crystallographic Data Center under
CCDC 801336. These data can be obtained free of
charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
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[17] Crystal data for compound 2s: C16H17NO5; MW=
303.31, triclinic, space group P-1, final R indices [I>
2s(I)], R1=0.0372, wR2=0.0972, R indices (all data)
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R1=0.0468,
wR2=0.1035,
a=8.1581(6) ꢃ,
b=
9.5889(7) ꢃ, c=10.4998(8) ꢃ, a=1098, b=1068, g=
958, V=733.42(9) ꢃ3, T=296(2) K, Z=2, reflections
collected/unique 7843/2585 (Rint =0.0396), number of
observations [> 2s(I)] 2135, parameters: 199. Supple-
mentary crystallographic data have been deposited at
the Cambridge Crystallographic Data Centre under
CCDC 801335. These data can be obtained free of
charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
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[10] a) B. M. Trost, P.-Y. Michellys, V. J. Gerusz, Angew.
Chem. 1997, 109, 1837; Angew. Chem. Int. Ed. Engl.
1997, 36, 1750; for some reports about hydropallada-
tion of allenes, see: b) Y. Yamamoto, M. Al-Masum, N.
Asao, J. Am. Chem. Soc. 1994, 116, 6019; c) M.
Meguro, S. Kamijo, Y. Yamamoto, Tetrahedron Lett.
1996, 37, 7453.
[11] For a recent report from this group, see: X. Jiang, Q.
Yang, Y. Yu, C. Fu, S. Ma, Chem. Eur. J. 2009, 15, 7283.
[12] S. R. Wilson, C. E. Augelli, Org. Synth. 1990, 68, 210.
[13] For palladium-catalyzed allylations with stabilized nu-
cleophiles via C-attack, see: a) J. Tsuji, I. Minami, I.
Shimizu, Tetrahedron Lett. 1983, 24, 1793; b) Y. Huang,
X. Lu, Tetrahedron Lett. 1988, 29, 5663; c) M. Ahmar,
B. Zazes, J. Gore, Tetrahedron Lett. 1984, 25, 4505;
d) M. Ahmar, J. J. Barieux, B. Zazes, J. Gore, Tetrahe-
dron 1987, 43, 513; e) C. Kammerer, G. Prestat, D.
Madec, G. Poli, Chem. Eur. J. 2009, 15, 4224.
[18] Crystal data for compound 2u: C17H19BrO3; MW=
351.23, monoclinic, space group C2/c, final R indices
[I> 2s(I)], R1=0.0295, wR2=0.0717, R indices (all
data) R1=0.0386, wR2=0.0769, a=27.5708(9) ꢃ, b=
6.0338(2) ꢃ, c=19.6616(7) ꢃ, a=908, b=1028, g=908,
V=3200.57(19) ꢃ3, T=296(2) K, Z=8, reflections col-
lected/unique 17661/2809 (Rint =0.0285), number of ob-
servations [> 2s(I)] 2354, parameters: 190. Supple-
mentary crystallographic data have been deposited at
the Cambridge Crystallographic Data Centre under
CCDC 801334. These data can be obtained free of
charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[19] Crystal data for compound 2x: C16H17NO5; MW=
303.31, triclinic, space group P-1, final R indices [I>
2s(I)], R1=0.0357, wR2=0.0912, R indices (all data)
R1=0.0406,
wR2=0.0967,
a=8.8711(5) ꢃ,
b=
9.5519(5) ꢃ, c=10.3514(6) ꢃ, a=658, b=708, g=818,
V=743.99(7) ꢃ3, T=296(2) K, Z=2, reflections col-
lected/unique 8679/2618 (Rint =0.0155), number of ob-
servations [> 2s(I)] 2316, parameters: 199. Supple-
mentary crystallographic data have been deposited at
the Cambridge Crystallographic Data Centre under
CCDC 822025. These data can be obtained free of
charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
[14] For palladium-catalyzed allylations with stabilized nu-
cleophiles via O-attack, see: a) J. Tsuji, Y. Kabayashi,
H. Kataoka, T. Takahashi, Tetrahedron Lett. 1980, 21,
1475; b) ref.[7g]; c) ref.[7j]
[15] For reviews, see: a) C. G. Frost, J. Howarth, J. M. Wil-
liams, Tetrahedron: Asymmetry 1992, 3, 1089; b) B. M.
Trost, D. L. Van Vranken, Chem. Rev. 1996, 96, 395.
[16] Crystal data for compound 2m: C80H68Br4O12; MW=
1540.98, triclinic, space group P-1, final R indices [I>
2s(I)], R1=0.0759, wR2=0.1538, R indices (all data)
[20] a) F.-Y. Yang, M.-Y. Wu, C.-H. Cheng, J. Am. Chem.
Soc. 2000, 122, 7122; b) Z. Gu, X. Wang, W. Shu, S.
Ma, J. Am. Chem. Soc. 2007, 129, 10948.
[21] The terminal allenols were prepared from terminal al-
kynols according to the known procedure: J. Kuang, S.
Ma, J. Org. Chem. 2009, 74, 1763.
1774
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Adv. Synth. Catal. 2011, 353, 1763 – 1774