A novel highly regio- and diastereoselective haloamination of alkenes catalyzed by divalent palladium

Article abstract of DOI:10.1016/j.tetlet.2003.12.109

From the readily available allylic alcohols or allylic amines, a novel Pd(II)-CuCl₂-catalyzed haloamination reaction of alkenes with high chemo-, regio-, and diastereo-selectivity was developed. The reaction proceeds through trans-aminopalladat

Full text of DOI:10.1016/j.tetlet.2003.12.109

Tetrahedron
Letters
Tetrahedron Letters 45 (2004) 1785–1788
A novel highly regio- and diastereoselective haloamination
of alkenes catalyzed by divalent palladium
*
Aiwen Lei, Xiyan Lu and Guosheng Liu
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
3
54 Fenglin Lu, Shanghai 200032, China
Received 14 July 2003; revised 11 November 2003; accepted 10 December 2003
2
Abstract—From the readily available allylic alcohols or allylic amines, a novel Pd(II)–CuCl -catalyzed haloamination reaction of
alkenes with high chemo-, regio-, and diastereo-selectivity was developed. The reaction proceeds through trans-aminopalladation of
alkenes, followed by oxidative cleavage of the carbon–palladium bond with retention of configuration.
Ó 2003 Elsevier Ltd. All rights reserved.
In Pd(II)-catalyzed reaction, the key step is quenching
OH TsNCO
THF
OCONHTs
2a
the carbon–palladium bond to regenerate the Pd(II)
species making the reaction catalytically possible. In a
series of our works initiated with nucleopalladation, we
1
a
X
O
1
O
O
have successfully used b-heteroatom elimination, oxi-
Pd(OAc)2
2
3
X
dative cleavage, and protonolysis reaction to quench
the carbon–palladium bonds. Herein, we wish to report
our recent results of a novel haloamination reaction of
alkenes initiated by aminopalladation followed by oxi-
dative cleavage of the carbon–palladium bond with
O
N
CuX , LiX
O
N
O
N
2
Ts
THF
Ts
X = Cl 3a
X = Br 3b
Ts
62%
63%
4
5
Scheme 1.
CuCl as a novel entry in the field of oxidative multi-
2
4
functionalization of alkenes.
formed, which may be due to the presence of excess
halide ions.
The reaction of O-allylic carbamate 2a (1 mmol), which
was formed from the reaction of allylic alcohol and
p-toluenesulfonyl isocyanate (TsNCO) in THF (5 mL),
3e
Allylic amines can also be used as substrates to afford
corresponding imidazolidinones easily under similar
condition. As compared with allylic primary amine 1g
2
in the presence of a catalytic amount of Pd(OAc) ,
CuCl (5 mmol), and LiCl (2 mmol) at room tempera-
2
ture afforded the chloroamination product, oxazolidi-
none 3a, in 62% yield. Under the similar condition,
using CuBr /LiBr instead of CuCl /LiCl, the bromo-
(Table 1, entries 5 and 6), the reactions of the N-benzyl
allylic amine 1i gave almost quantitative yields indicat-
ing that the substituents attached on the nitrogen atom
are important in the cyclization (Table 1, entries 7 and
2
2
amination product 3b was obtained in 63% yield
Scheme 1). The regioisomeric product 4 formed by the
attack of the nitrogen nucleophile to the terminal car-
(
8).
5
bon atom of alkene was not observed (Scheme 1). In
addition, no b-hydride elimination product 5 was
It is noteworthy that the reaction can be carried out in a
one-pot manner via the in situ generation of the
N-tosyl-carbamates or ureas from the corresponding
6
allylic alcohols or allylic amines and TsNCO, followed
by the Pd(II)-catalyzed reaction. Substituted allylic
alcohols 1 were examined under the similar conditions
(Table 1), and they all gave exclusively the haloamina-
Keywords: Carbopalladation; Coupling reaction; Divalent palladium;
b-Heteroatom elimination.
*
Corresponding author. Tel.: +86-21-64163300x3333; fax: +86-21-6-
166128; e-mail: xylu@mail.sioc.ac.cn
7
4
tion products. Using the substrates, which contain a
0
040-4039/$ - see front matter Ó 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2003.12.109

1786
A. Lei et al. / Tetrahedron Letters 45 (2004) 1785–1788
Table 1. Haloamination of alkenes catalyzed by divalent palladium
a
complex
1
. TsNCO, THF
. Pd(OAc)2
O
OH
X
2
O
N
Ts
R
Y
CuX , LiX
2
YH 1. TsNCO, THF
X
8
X = Cl 9a, 77%
X = Br 9b, 68%
2
. Pd(OAc)2
O
N
Ts
R
CuX , LiX
2
1
trans-3
Scheme 3.
Entry
Substrates
Y
Products
b
1
R
X
3
Yield
(
C H
5 11
%)
O
OH 1. TsNCO, THF
c
1
2
3
4
5
6
7
8
1c
1c
1e
1e
1g
1g
1i
Me
Me
n-C
n-C
H
O
O
Cl
Br
Cl
Br
Cl
Br
Cl
Br
3c
3d
3e
3f
3g
3h
3i
66
65
64
70
86
78
97
93
X
2
. Pd(OAc)2
O
N
Ts
C H
5
11
CuX , LiX
2
5
5
H
H
11
O
O
(R)-1e
(4S,5R)-3e
11
NH
NH
NBn
NBn
H
Scheme 4.
H
1i
H
3j
a
Substrate (1 mmol) reacted with TsNCO (1.1 mmol) in THF at rt for
0 min under Ar. Then cupric halide (5 mmol), lithium halide
1
R
O
(
2 mmol), and Pd(OAc)
2
(0.05 mmol) were added, the reaction was
OCONHTs
X
monitored by TLC.
Isolated yield.
O
N
b
c
Pd(II)
R
Ts
1
2
The trans/cis ratio was determined by the H NMR spectra.
CuX , LiX
2
PdII
substituent at the allylic position, the trans-disubstituted
products were unambiguously obtained as determined
by H NOESY spectra of 3c and X-ray diffraction study
8
of 3d.
R
O
PdII
H
H
Pd(II)
O
H
Ts
1
H
O
N
N
R
O
Ts
N
O
1
R
Ts
H
1
O
1
0
When the 3-substituted allyl alcohol 6 was used as the
substrate, only single diastereoisomeric product 7 was
obtained in 50% yield. The X-ray diffraction result of 7
showed that the oxidative cleavage of carbon–palladium
bond occurred with retention of configuration of the
carbon atom if the trans-aminopalladation happened in
X
X
R
R
R
O
O
Pd
or
O
O
N
Ts
O
N
Ts
O
N
Ts
9;10
1
3
14
the first step (Scheme 2), which is consistent with our
previous report.
1
2
2d
Scheme 5.
Using this method, oxazindinones 9 were obtained as
the corresponding haloamination products of alkenes in
excellent yield when the homoallylic alcohol 8 was used
as the substrates (Scheme 3).
the divalent palladium species; then followed by the
oxidative cleavage of the carbon–palladium bond in the
presence of cupric halide and lithium halide (Scheme
When the readily available homochiral allylic alcohol
(R)-1e was used as the substrate, (4S,5R)-3e (>97% ee)
was easily obtained (Scheme 4).
2;11
5
).
During our observation, only five-membered
5
cyclic intermediate 11 was formed. When the substrates
contain a substituent at allylic position, the addition of
the nucleophile to the carbon–carbon double bond from
the opposite side of the substituent occurred (interme-
diate 10), which determined the trans-selectivity of the
A speculated mechanism is shown in Scheme 5: Firstly, a
carbon–palladium bond was formed from the intramo-
10
lecular trans-nucleopalladation to alkenes activated by
12
reaction. The reaction is highly selective for the oxi-
dative cleavage reaction of the carbon–palladium bond,
no b-hydride elimination products (13 and 14) were
found. The presence of excess halide ions in the reaction
may inhibit the b-hydride elimination of the carbon–
palladium bond making the reaction highly chemo-
Cl
Pd(OAc)2
H
OCONHTs
H
O
NTs
CuCl , LiCl
3e
2
selective.
THF
O
7
In summary, we developed an oxidative multifunction-
alization of alkenes via the palladium(II)-catalyzed
reaction from readily available allylic alcohols or allylic
6
Scheme 2.

A. Lei et al. / Tetrahedron Letters 45 (2004) 1785–1788
1787
3
5
þ
amines, from which oxazolidinones and imidazolid-
inones are easily obtained from corresponding sub-
strates. Moreover, utilizing the readily available
homochiral allylic alcohol as the starting material, the
highly optically active oxazolidinones, which are the
precursor of amino alcohols, are easily obtained
implying the synthetic utility of this reaction.
290 ( M +1), 225, 176, 155, 139, 91, 65; Anal. Calcd for
S: C, 45.60; H, 4.17; N, 4.83. Found: C,
4
11 4
C H12ClNO
5.54; H, 4.03; N, 4.84.
1
3
b: mp 147–149 °C; H NMR (300 MHz, CDCl
3
) d 7.90 (d,
J ¼ 8.4 Hz, 2H), 7.30 (d, J ¼ 8.3 Hz, 2H), 4.70–4.62 (m,
1
2
1
1
H), 4.44–4.35 (m, 1H), 4.24–4.15 (m, 1H), 3.73–3.54 (m,
H), 2.34 (s, 3H); IR (neat) 3039, 2973, 1768, 1596, 1496,
471, 1435, 1390, 1361, 1336, 1325, 1207, 1173, 1123, 1091,
ꢀ
1
069, 821, 754, 670, 618, 582, 573, 541 cm ; MS m=e 336
M +1), 334 ( M +1), 271, 269, 254, 176, 155, 139, 91,
8
1
þ
79
þ
(
6
4
3
5; Anal. Calcd for C11H12BrNO S: C, 39.54; H, 3.62; N,
4
.19. Found: C, 39.54; H, 3.39; N, 4.19.
Acknowledgements
1
c: mp 105–106 °C; H NMR (300 MHz, CDCl
3
) d 7.90 (d,
J ¼ 8.4 Hz, 2H), 7.31 (d, J ¼ 8.4 Hz, 2H), 4.52 (dq, J ¼ 3.4,
The Major State Basic Research Program (Grant No.
G2000077502-A). We thank the National Natural Sci-
ences Foundation of China and Chinese Academy of
Sciences for financial support.
6
.4 Hz, 1H), 4.14 (ddd, J ¼ 3.4, 3.2, 7.2 Hz, 1H), 3.84 (dd,
J ¼ 3.2, 11.7 Hz, 1H), 3.75 (dd, J ¼ 7.2, 11.7 Hz, 1H), 2.40
(
s, 3H), 1.32 (d, J ¼ 6.4 Hz, 3H); IR (neat) 1789, 1596,
1
7
450, 1360, 1329, 1209, 1170, 1145, 1087, 1047, 816, 755,
ꢀ
1
37
þ
35, 665, 578, 542 cm ; MS m=e 306 ( M +1), 304
3
5
þ
(
M +1), 239, 190, 155, 146, 91, 65; Anal. Calcd for
S: C, 47.45; H, 4.65; N, 4.61. Found: C,
47.51; H, 4.68; N, 4.40.
12 4
C H14ClNO
References and notes
1
3
3
d: mp 126–127 °C; H NMR (300 MHz, CDCl ) d 7.96 (d,
1
. (a) Ma, S.; Lu, X. J. Chem. Soc., Chem. Commun. 1990,
J ¼ 8.2 Hz, 2H), 7.38 (d, J ¼ 8.5 Hz, 2H), 4.55 (ddq,
J ¼ 0.7, 3.2, 5.8 Hz, 1H), 4.22 (ddd, J ¼ 0.6, 3.0, 8.1 Hz,
1H), 3.78 (ddd, J ¼ 0.6, 2.8, 6.7 Hz, 1H), 3.2 (ddq, J ¼ 0.7,
8.1, 10.6 Hz, 1H), 2.37 (s, 3H), 1.39 (d, J ¼ 5.8 Hz, 3H); IR
(neat) 3046, 2988, 1786, 1595, 1358, 1204, 1167, 1137,
7
5
3
1
5
(
1
1
33–734; (b) Ma, S.; Lu, X. J. Org. Chem. 1991, 56, 5120–
125; (c) Ma, S.; Zhu, G.; Lu, X. J. Org. Chem. 1993, 58,
692–3696; (d) Ma, S.; Lu, X. J. Organometal. Chem.
993, 447, 305–309; (e) Ma, S.; Lu, X. J. Org. Chem. 1993,
8, 1245–1250; (f) Zhu, G.; Ma, S.; Lu, X. J. Chem. Res.
S) 1993, 366–367; (g) Zhu, G.; Lu, X. Organometallics
995, 14, 4899–4904; (h) Zhu, G.; Lu, X. J. Org. Chem.
995, 60, 1087–1089.
ꢀ
1
1085, 104, 816, 753, 672, 660, 574, 541 cm ; MS m=e 350
8
1
79
( M+1), 348 ( M+1), 285, 283, 190, 155, 91, 65; Anal.
Calcd for C12 S: C, 41.39; H, 4.05; N, 4.02.
Found: C, 41.56; H, 4.01; N, 3.88.
H14BrNO
4
1
2
3
. (a) Ji, J.; Lu, X. Synlett 1993, 745–747; (b) Ji, J.; Zhang,
C.; Lu, X. J. Org. Chem. 1995, 60, 1160–1169; (c) Ji, J.; Lu,
X. Tetrahedron 1994, 50, 9067–9078;
d) Zhu, G.; Ma, S.; Lu, X.; Huang, Q. J. Chem. Soc.,
Chem. Commun. 1995, 271–273; (e) Zhu, G.; Lu, X.
J. Organomet. Chem. 1996, 508, 83–90.
. (a) Wang, Z.; Lu, X. Chem. Commun. 1996, 535–536; (b)
Wang, Z.; Lu, X. J. Org. Chem. 1996, 61, 2254–2255; (c)
Wang, Z.; Lu, X. Tetrahedron Lett. 1997, 38, 5213–5216;
d) Wang, Z.; Lu, X.; Lei, A.; Zhang, Z. J. Org. Chem.
998, 63, 3806–3807; (e) Wang, Z.; Zhang, Z.; Lu, X.
Organometallics 2000, 19, 775–780.
3e: oil; H NMR (300 MHz, CDCl
3
) d 7.94 (d, J ¼ 8.4 Hz,
2H), 7.37 (d, J ¼ 8.4 Hz, 2H), 4.70–4.57 (m, 1H), 4.43 (dt,
J ¼ 3.4, 6.4 Hz, 1H), 4.30–4.23 (m, 1H), 3.86–3.84 (m, 1H),
2.45 (s, 3H), 1.63–1.56 (m, 2H), 1.34–1.26 (m, 6H); 0.89 (t,
J ¼ 6.4 Hz, 3H); IR (neat) 2956, 2930, 1781, 1596, 1368,
(
ꢀ1
37
þ
1174, 1138, 1091, 665 cm ; MS m=e 362 ( M +1), 360
3
5
þ
( M +1), 310, 246, 155, 108, 91, 65; Anal. Calcd for
S: C, 53.40; H, 6.16; N, 3.89. Found: C,
16 4
C H22ClNO
53.80; H, 6.48; N, 3.91.
1
3f: oil; H NMR (300 MHz, CDCl
(
1
3
) d 7.89 (d, J ¼ 8.3 Hz,
2H), 7.30 (d, J ¼ 8.5 Hz, 2H), 4.33 (dt, J ¼ 3.0, 6.3 Hz, 1H),
4.18 (dt, J ¼ 2.9, 7.9 Hz, 1H), 3.68 (dd, J ¼ 2.8, 10.6 Hz,
1H), 3.56 (dd, J ¼ 7.9, 10.6 Hz, 1H), 2.38 (s, 3H), 1.54–1.49
(m, 2H); 1.28–1.19 (m, 6H), 0.80 (t, J ¼ 6.7 Hz, 3H); IR
(neat) 2950, 2927, 2859, 1782, 1596, 1461, 1371, 1134,
1090, 1044, 814, 752, 704, 668, 575, 545 cm ; MS m=e 406
81 79
( M+1), 404 ( M+1), 310, 260, 246, 155, 108, 91, 65;
HRMS calcd for
403.0468.
4
. (a) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980,
1
02, 5974–5976; (b) Jacobsen, E. N.; Marko, I.; Mungall,
W. S.; Schroder, G.; Sharpless, K. B. J. Am. Chem. Soc.
988, 110, 1968–1970.
. In the absence of cupric halide, the six-membered
cyclic intermediate 9 was reported to be the possible
intermediate: Lei, A.; Lu, X. Org. Lett. 2000, 2, 2357–
ꢀ1
1
5
C
16
H22BrNO
4
S: 403.0453, found:
1
2
360.
3g: mp 167.5–168 °C; H NMR (300 MHz, CDCl
3
) d 7.84
6
. Tamaru, Y.; Kimura, M.; Tanaka, S.; Kure, S.; Yoshida,
Z.-I. Bull. Chem. Soc. Jpn. 1994, 67, 2838–2849.
. Typical procedure for the reaction: Compound 1c
1.0 mmol) was reacted with TsNCO (1.1 mmol) in THF
5 mL) for 10 min at rt under N ; then, Pd(OAc)
0.05 mmol), LiBr (2.0 mmol), and CuCl (5.0 mmol) were
added and the reaction was stirred at rt. After the reaction
was complete as monitored by TLC, the solvent was
removed and the residue was purified by column chroma-
(d, J ¼ 8.3 Hz, 2H), 7.26 (d, J ¼ 8.4 Hz, 2H), 5.89 (br, 1H),
4.54–4.46 (m, 1H), 3.84 (dd, J ¼ 3.1, 11.2 Hz, 1H), 3.73
(dd, J ¼ 7.6, 11.2 Hz, 1H), 3.53 (t, J ¼ 9.4 Hz, 1H), 3.36
(ddd, J ¼ 1.0, 4.0, 9.5 Hz, 1H), 2.37 (s, 3H); IR (neat) 3250,
7
(
(
(
ꢀ
1
1743, 1363, 1163, 1090, 664, 577, 541 cm ; MS m=e 291
37 35
2
2
þ
þ
( M +1), 289 ( M +1), 239, 224, 175, 155, 139, 91, 65;
Anal. Calcd for C11 S: C, 45.76; H, 4.54; N,
9.70. Found: C, 45.54; H, 4.41; N, 9.65.
2
2 3
H13ClN O
1
3h: mp 199–200 °C; H NMR (300 MHz, CDCl
3
) d 7.87 (d,
tography on silica gel to give product 3c with 66% yield.
1
J ¼ 8.4 Hz, 2H), 7.28 (d, J ¼ 8.0 Hz, 2H), 5.22 (br, 1H),
4.57–4.49 (m, 1H), 3.76 (dd, J ¼ 3.0, 10.4 Hz, 1H), 3.62–
3.52 (m, 2H), 3.34 (ddd, J ¼ 1.1, 8.1, 9.6 Hz, 1H), 2.37 (s,
3H); IR (neat) 3250, 3138, 1741, 1364, 1171, 1070, 671,
3
a: mp 159–160 °C; H NMR (300 MHz, CDCl
3
) d 7.89 (d,
J ¼ 8.3 Hz, 2H), 7.30 (d, J ¼ 8.2 Hz, 2H), 4.72–4.63 (m,
1
9
H), 4.38 (dd, J ¼ 9.0, 8.6 Hz, 1H), 4.25 (dd, J ¼ 3.9,
.1 Hz, 1H), 3.84 (dd, J ¼ 6.0, 11.7 Hz, 1H), 3.79 (dd,
ꢀ
1
81
þ
79
þ
574 cm ; MS m=e 335 ( M +1), 333 ( M +1), 310, 268,
239, 175, 155, 139, 91, 65; Anal. Calcd for
C O
39.50; H, 3.78; N, 8.41.
J ¼ 3.1, 11.7 Hz, 1H), 2.39 (s, 3H); IR (neat) 3039, 2973,
1
8
769, 1595, 1441, 1389, 1359, 1329, 1209, 1172, 1132, 1089,
20, 757, 672, 607, 573, 543 cm ; MS m=e 292 ( M +1),
11
H13BrN
2
3
S: C, 39.65; H, 3.93; N, 8.41. Found: C,
ꢀ1
37
þ

1788
A. Lei et al. / Tetrahedron Letters 45 (2004) 1785–1788
1
3
(
3
i: mp 179–179.5 °C; H NMR (300 MHz, CDCl
d, J ¼ 8.3 Hz, 2H), 7.27 (d, J ¼ 8.0 Hz, 2H), 7.23–7.19 (m,
H), 7.28–7.03 (m, 2H), 4.43–4.40 (m, 1H), 4.27 (d,
3
) d 7.89
239, 203, 190, 155, 146, 91, 65; Anal. Calcd for
12 4
C H14ClNO S: C, 47.45; H, 4.65; N, 4.61. Found: C,
47.76; H, 4.91; N, 4.58.
1
9b: oil; H NMR (300 MHz, CDCl
J ¼ 14.9 Hz, 1H), 4.22 (d, J ¼ 14.9 Hz, 1H), 3.81–3.68 (m,
3
) d 7.92 (d, J ¼ 8.3 Hz,
2
2
1
3
C
5
3
(
3
H), 3.33 (t, J ¼ 9.5 Hz, 1H), 3.12 (dd, J ¼ 4.1, 9.5 Hz, 1H),
2H), 7.33 (d, J ¼ 8.5 Hz, 2H), 4.84–4.79 (m, 1H), 4.37–4.30
(m, 2H), 3.88 (dd, J ¼ 3.6, 0.5 Hz, 1H), 3.50 (t, J ¼ 10.4 Hz,
1H), 2.57–2.49 (m, 1H), 2.44 (s, 3H) 2.34–2.15 (m, 1H); IR
(neat) 2968, 2925, 1734, 1596, 1409, 1351, 1270, 1172,
.38 (s, 3H); IR (neat) 3054, 3024, 2922, 1744, 1721, 1440,
362, 1170, 1105, 588, 546 cm ; MS m=e 381 ( M +1),
79 ( M +1), 329, 314, 265, 263, 91, 65; Anal. Calcd for
ꢀ
1
37
þ
3
5
þ
ꢀ
1
81
þ
18
H19ClN
2
O
7.21; H, 5.03; N, 7.31.
3
S: C, 57.06; H, 5.05; N, 7.39. Found: C,
1087, 814, 667 cm
;
MS m=e 350 ( M +1), 348
( M +1), 285, 283, 190, 155, 146, 118, 91, 65; Anal.
Calcd for C12 S: C, 41.39; H, 4.05; N, 4.02.
7
9
þ
1
j: mp 203–203.8 °C; H NMR (300 MHz, CDCl
3
) d 7.98
H14BrNO
4
d, J ¼ 8.4 Hz, 2H), 7.40 (d, J ¼ 8.4 Hz, 2H), 7.32–7.27 (m,
Found: C, 41.58; H, 4.15; N, 3.65.
H), 7.15–7.1203 (m, 2H), 4.52–4.45 (m, 1H), 4.37 (d,
3 2
8. There is strong NOE between 4-H and 5-CH , 4-CH Cl
J ¼ 14.9 Hz, 1H), 4.29 (d, J ¼ 14.9 Hz, 1H), 3.76 (dd,
and 5-H in the NOESY spectra of compound 3c. In
addition, there is no NOE between 4-H and 5-H. The
direct evidence for the stereo-configuration is the X-ray
J ¼ 2.9, 10.4 Hz, 1H), 3.61 (d, J ¼ 7.7, 10.4 Hz, 1H), 3.42
(
t, J ¼ 9.5 Hz, 1H), 3.16 (dd, J ¼ 4.3, 9.6 Hz, 1H), 2.47 (s,
3
1
5
2
5
7
H); IR (neat) 3054, 3024, 2922, 1743, 1594, 1493, 1486,
447, 1439, 1360, 1175, 1332, 1265, 1188, 764, 702, 663,
2 3
crystallography of 3d in which 4-CH Br and 5-CH are in
trans-configuration.
ꢀ
1
81
þ
79
þ
86, 546 cm ; MS m=e 425 ( M +1), 423 ( M +1), 358,
67, 265, 155, 91, 65; Anal. Calcd for C18 S: C,
1.07; H, 4.52; N, 6.62. Found: C, 51.23; H, 4.50; N, 6.54.
9. Deposit number of 3d from Crystallographic Data Cen-
tre: CCDC 212346. Deposit number of 7 from Crys-
tallographic Data Centre: CCDC 212345. Copies of
the data can be obtained free of charge on applica-
tion to CCDC, 12, Union Road, Cambridge CB21EZ,
UK; fax: +44-1223-336-033; e-mail: deposit@ccdc.cam.
ac.uk.
10. N-Tosyl carbamates could be used as the efficient nucleo-
philes in the trans-aminopalladation reaction of alkenes or
alkynes (a) Trost, B. M.; Vranken, D. L.-V. Angew.
Chem., Int. Ed. Engl. 1992, 31, 228–230; (b) Tamaru, Y.;
Kimura, M. Synlett 1997, 749–757.
11. (a) Daub, G. W. Prog. Inorg. Chem. 1977, 22, 409–423; (b)
B €a ckvall, J. E. Acc. Chem. Res. 1983, 16, 335–342; (c)
Wong, P. K.; Still, J. K. J. Organomet. Chem. 1974, 70,
121–134; (d) Heck, R. F. Organotransitionmetal Chemis-
try; Academic: New York, 1974; p 110.
H
2 3
19BrN O
1
: mp 155–155.5 °C: H NMR (300 MHz, CDCl
3
) d 7.96
(
d, J ¼ 8.4 Hz, 2H), 7.38 (d, J ¼ 8.4 Hz, 2H), 4.71 (ddd,
J ¼ 3.6, 3.7, 8.7 Hz, 1H), 4.65 (dq, J ¼ 3.9, 6.7 Hz, 1H),
4
2
2
.45 (dd, J ¼ 3.3, 9.7 Hz, 1H), 4.35 (d, J ¼ 8.6, 9.7 Hz, 1H),
.46 (s, 3H), 1.41 (d, J ¼ 6.7 Hz, 3H); IR (neat) 3054, 3024,
ꢀ1
37
þ
922, 1773, 1377, 1178 cm ; MS m=e 306 ( M +1), 304
M +1), 240, 176, 155, 91, 65; Anal. Calcd for
3
5
þ
(
C H14ClNO S: C, 47.45; H, 4.65; N, 4.61. Found: C,
12 4
4
9
2
7.58; H, 4.61; N, 4.45.
1
a: oil; H NMR (300 MHz, CDCl
H), 7.33 (d, J ¼ 8.2 Hz, 2H), 4.82–4.79 (m, 1H), 4.39 (dt,
3
) d 7.92 (d, J ¼ 8.4 Hz,
J ¼ 3.4, 11.5 Hz, 1H), 4.33–4.29 (m, 1H), 4.00 (ddd,
J ¼ 0.7, 3.6, 11.3 Hz, 1H), 3.68 (dd, J ¼ 9.8, 11.2 Hz,
1
1
6
H), 2.51–2.43 (m, 4H), 2.22–2.14 (m, 1H); IR (neat) 2924,
738, 1657, 1596, 1400, 1358, 1280, 1170, 1087, 814, 667,
12. Tamaru, Y.; Hojo, M.; Higashimura, H.; Yoshida, Z.
J. Am. Chem. Soc. 1988, 110, 3994–4002.
ꢀ1
37
þ
35
þ
13, 539 cm ; MS m=e 306 ( M +1), 304 ( M +1), 268,