PdII-Catalyzed Cyclization of Allylic N-Tosylcarbamates
J . Org. Chem., Vol. 67, No. 3, 2002 979
(d, J ) 6.7 Hz, 2H), 3.20 (s br, 1H), 2.90 (s br, 1H); IR (neat)
ν 3370, 3030, 1454, 1103, 1028, 739, 699 cm-1; MS m/e 209
(M+ + 1), 181, 173, 143, 129, 91(100), 83, 69; HRMS (M - H2O)
calcd for C12H14O2 190.0994, found 190.1010.
N-(p-Tolu en esu lfon yl)-5-p en tyl-4-vin yl-2-oxa zolid in o-
n e (2g): mp 61.0-61.5 °C; 1H NMR (CDCl3) δ 7.85 (d, J ) 8.4
Hz, 2H), 7.27 (d, J ) 8.2 Hz, 2H), 5.79-5.67 (m, 1H), 5.37 (d,
J ) 17.1 Hz, 1H), 5.30 (d, J ) 10.1 Hz, 1H), 4.45 (dd, J ) 4.3,
8.2 Hz, 1H), 4.14 (dt, J ) 6.4, 4.4 Hz, 1H), 2.38 (s, 3H), 1.61-
1.19 (m, 8H), 0.81 (t, J ) 6.8 Hz, 3H); IR (neat) ν 2958, 2931,
2862, 1784, 1371, 1175, 665 cm-1; MS (m/e) 338 (M++1), 173,
155, 119, 108, 91, 82, 65, 41. Anal. Calcd for C17H23NO4S: C,
60.51; H, 6.87; N, 4.15. Found: C, 60.41; H, 6.75; N, 4.09.
(E)-N-(p -Tolu en esu lfon yl)-4-(2′-isop r op ylvin yl)-2-ox-
a zolid in on e (5b): oil; 1H NMR (CDCl3) δ 7.92 (d, J ) 8.4
Hz, 2H), 7.32 (d, J ) 8.4 Hz, 2H), 5.90 (dd, J ) 6.2, 15.3 Hz,
1H), 5.30 (ddd, J ) 15.4, 9.0, 1.4 Hz, 1H), 4.89 (dt, J ) 3.4,
8.3 Hz, 1H), 4.49 (t, J ) 8.7 Hz, 1H), 4.02 (dd, J ) 3.4, 8.7 Hz,
1H), 2.45 (s, 3H), 2.40-2.30 (m, 1H), 0.99 (d, J ) 6.8 Hz, 6H);
(E)-5-Ben zyloxyp en t-2-en e-1,4-d iol ((E)-6l): oil; 1H NMR
(CDCl3) δ 7.35-7.25 (m, 5H), 5.79 (dt, J ) 15.6, 5.2 Hz, 1H),
5.51 (dd, J ) 15.6, 5.9 Hz, 1H), 4.57 (s, 2H), 4.38 (m, 1H), 4.15
(s, 2H), 3.53 (dd, J ) 9.6, 3.2 Hz, 1H), 3.36 (m, 1H), 2.55 (s br,
1H), 1.63 (s br, 1H); IR (neat) ν 3370, 3032, 2864, 1454, 1098,
1003, 740, 699 cm-1; MS m/e 208 (M+), 190, 177, 145, 107, 91
(100), 87, 69; HRMS (M - H2O) calcd for C12H14O2 190.0994,
found 190.0983.
(Z)-(4R,5R)-5,6-O-isopr opyliden eh ex-2-en e-1,4-diol (6n ).
To a solution of CuI (13.6 g, 72 mmol) in a mixture of THF
(100 mL) and Me2S (20 mL) was added the Grignard reagent
12 (60 mmol) in THF (30 mL) at -78 °C, and the mixture was
stirred for 5 min at -78 °C under argon. (R)-2,3-Isopro-
pylideneglyceraldehyde (6.3 g, 48 mmol) was then added, and
the mixture was gradually warmed to room temperature. After
the mixture was stirred for 2 h, saturated NH4Cl (30 mL)
solution was added, and the mixture was extracted with ethyl
acetate. The combined extracts were dried (MgSO4), filtered,
and evaporated. The crude oil was purified by column chro-
matography on silica gel (ethyl acetate/petrolum ether ) 1/5)
to give 13 (12.3 g, yield 86%) as an oil: 1H NMR (CDCl3) δ
4.22 (s, 2H), 4.20 (d, J ) 1.4 Hz, 1H), 4.06 (ddd, J ) 6.5, 5.4,
1.4 Hz, 1H), 3.98 (dd, J ) 6.5, 8.5 Hz, 1H), 3.77 (dd, J ) 5.4,
8.5 Hz, 1H), 2.35 (s, br, 1H), 1.34 (s, 3H), 1.26 (s, 3H), 0.79 (s,
9H), 0.01 (s, 6H); IR (neat) ν 3439, 1473, 1464, 1373, 1256,
1074, 838, 780 cm-1; MS m/e 285, 185, 111, 101, 75 (100), 59,
43. Anal. Calcd for C15H28O4Si: C, 59.96; H, 9.39. Found: C,
59.64; H, 9.07.
IR (neat) ν 1785, 1598, 1372, 1174, 1092, 815, 667, 580 cm-1
;
MS m/e 310 (M+ + 1), 266, 240, 202, 155, 139, 110, 91 (100),
65. Anal. Calcd for C15H19NO4S: C, 58.23; H, 6.19; N,4.53.
Found: C, 58.23; H, 6.08; N, 4.55.
Typ ica l P r oced u r e for th e Rea ction of 6. Compound 6
(0.5 mmol) was reacted with TsNCO (1.10 mmol) in THF (5
mL) for 10 min at room temperature under N2. Then Pd(OAc)2
(5 mol %) and LiBr (2 mmol) were added, and the mixture
was heated to reflux. After the reaction was complete as
monitored by TLC, the solvent was removed under vacuum
and the residue was purified by column chromatography on
silica gel (petroleum ether/ ethyl acetate) to give product 2.
N-(p -Tolu en esu lfon yl)-5-b en zyloxym et h yl-4-vin yl-2-
1
oxa zolid in on e (2l): oil; H NMR (CDCl3) δ 7.89 (d, J ) 8.3
Hz, 2H), 7.38-7.29 (m, 5H), 7.25 (d, J ) 8.3 Hz, 2H), 5.84 (ddd,
J ) 7.7, 10.0, 17.0 Hz, 1H), 5.45 (d, J ) 17.0 Hz, 1H), 5.37 (d,
J ) 10.0 Hz, 1H), 4.81 (dd, J ) 7.7, 3.9 Hz, 1H), 4.47 (s, 2H),
4.25 (dt, J ) 3.9, 3.5 Hz, 1H), 3.57 (t, J ) 3.5 Hz, 2H), 2.40 (s,
3H); IR (neat) ν 1782, 1364, 1272, 1174, 1091, 815, 666, 567
cm-1; MS (m/e) 388 (M+ + 1), 387, 181, 155, 126, 91 (100), 82,
65; HRMS calcd for C20H21NO5S 387.1100, found 387.1140.
(4S,5R,4′R)-N-(p-Tolu en esu lfon yl)-5-(2,2-d im eth yl-1,3-
To a solution of 13 (12 g, 40 mmol) in THF (100 mL) was
added dropwise TBAF (40 mL, 1.0 M) in THF at room
temperature, and the mixture was stirred. After the reaction
was complete as monitored by TLC, the solvent was removed
under vacuum and the residue was purified by column
chromatography on silica gel to give the alkynediol. The
alkynediol was hydrogenated with Ni(OAc)2/NaBH4 to give 6n
using the literature method.22 After purification by column
chromatography on silica gel (ethyl acetate/petrolum ether )
1/1), optically pure (4R,5R)-6n was obtained by recrystalliza-
tion (ethyl acetate/petroleum ether) at -20 °C as a colorless
d ioxola n -4-yl)-4-vin yl-2-oxa zolid in on e (2n ): mp 120-121
1
°C; [R]20 ) -14.5 (c ) 2.40, CHCl3); H NMR (CDCl3) δ 7.94
D
(d, J ) 8.4 Hz, 2H), 7.34 (d, J ) 8.4 Hz, 2H), 5.93 (ddd, J )
7.7, 10.0, 17.0 Hz, 1H), 5.53 (d, J ) 17.0 Hz, 1H), 5.41 (d, J )
10.0 Hz, 1H), 4.84 (dd, J ) 7.7, 3.4 Hz, 1H), 4.18 (dt, J ) 7.7,
1.9 Hz, 1H), 4.14 (dd, J ) 3.4, 1.9 Hz, 1H), 4.04 (dd, J ) 8.6,
6.8 Hz, 1H), 3.84 (dd, J ) 8.6, 6.8 Hz, 1H), 2.45 (s, 3H), 1.27
(s, 3H), 1.10 (s, 3H); IR (neat) ν 1769, 1569, 1373, 1352, 1171,
1152, 1051, 820, 665 cm-1; MS (m/e) 352, 248, 171, 155, 146,
101, 91(100), 65, 43. Anal. Calcd for C17H21NO6S: C, 55.66;
H, 5.92; N, 4.10. Found: C, 55.57; H, 5.76; N, 3.81.
solid: mp 25-26 °C; [R]20 ) -5.1 (c ) 1.30, EtOH); 1H NMR
D
(CDCl3) δ 5.88 (ddt, J ) 5.7, 1.4, 1.2 Hz, 1H), 5.53 (ddt, J )
11.4, 8.0, 1.4 Hz, 1H), 4.41 (ddd, J ) 8.0, 6.4, 1.2 Hz, 1H),
4.32 (ddd, J ) 6.6, 5.7, 1.4 Hz, 1H), 4.21 (ddd, J ) 6.6, 5.7, 1.4
Hz, 1H), 4.09 (dt, J ) 6.4, 6.0 Hz, 1H), 4.00 (dd, J ) 8.4, 6.4
Hz, 1H), 3.76 (dd, J ) 8.4, 5.7 Hz, 1H), 2.85 (s, br, 1H), 2.64
(s, br, 1H), 1.46 (s, 3H), 1.37 (s, 3H); IR (neat) ν 3371, 1442,
1383, 1258, 1063, 864, 679 cm-1; MS m/e 173, 101 (100), 95,
83, 73, 67, 59, 55, 43. Anal. Calcd for C9H16O4: C, 57.43; H,
8.57. Found: C, 57.15; H, 8.32.
(4S,5R,1′R)-N-(p-Tolu en esu lfon yl)-5-(1′,2′-d ih yd r oxyl-
eth yl)-4-vin yl-2-oxa zolid in on e (14). CuCl2‚2H2O (340 mg,
2.0 mmol) was added to a solution of 2n (367 mg, 1.0 mmol)
in CH3CN (4 mL), and the solution was refluxed for ∼5 h. After
the reaction was complete as monitored by TLC, water (10 mL)
was added. The mixture was extracted with ethyl acetate (4
× 15 mL). The combined extracts were dried, filtered, and
concentrated. The residue was purified by column chromatog-
raphy on silica gel (petroleum ether/ethyl acetate ) 1:1) to give
Typ ica l P r oced u r e for th e Rea ction of 1. Compound 1
(0.5 mmol) was added to a solution of Pd(OAc)2 (5 mol %) and
LiBr (2 mmol) in THF, and the mixture was stirred at room
temperature. After the reaction was complete as monitored
by TLC, the solvent was removed under vacuum and the
residue was purified by column chromatography on silica gel
(petroleum ether/ethyl acetate ) 3/1) to give product 2a .
Typ ica l P r oced u r e for th e Rea ction of 3 a n d 4. Com-
pound 3 (0.5 mmol) was reacted with TsNCO (0.55 mmol) in
THF (5 mL) for 10 min at room temperature under N2. Then
Pd(OAc)2 (5 mol %) and LiBr (2 mmol) were added, and the
mixture was heated to reflux. After the reaction was complete
as monitored by TLC, the solvent was removed under vacuum
and the residue was purified by column chromatography on
silica gel (petroleum ether/ ethyl acetate) to give product 2.
Products 5 were obtained from 4 using the same procedure.
Compounds 2a ,9 2e,30 trans-2f,9 trans-2h ,9 and 5a 9 are
known compounds, and their spectroscopic data matched those
in the literature.
product 14 (310 mg, yield 93%) as an oil: [R]20 ) -40.8 (c )
D
2.66, CHCl3); 1H NMR (CDCl3) δ 7.90 (d, J ) 8.3 Hz, 2H), 7.33
(d, J ) 8.3 Hz, 2H), 5.86 (ddd, J ) 8.0, 10.1, 17.9 Hz, 1H),
5.50 (d, J ) 17.9 Hz, 1H), 5.38 (d, J ) 10.1 Hz, 1H), 4.94 (dd,
J ) 8.0, 4.2 Hz, 1H), 4.24 (dd, J ) 4.2, 2.4 Hz, 1H), 3.79 (d, J
) 4.7 Hz, 1H), 3.67 (s, br, 2H), 3.61 (d, J ) 4.7 Hz, 1H), 3.07
(s, br, 1H), 2.42 (s, 3H); IR ν (neat) 3519, 3410, 1781, 1597,
1370, 1174, 815, 668 cm-1; MS m/e 327, 210, 172, 155, 112, 91
(100), 68, 65. Anal. Calcd for C14H17NO6S: C, 51.64; H, 5.45;
N, 4.05. Found: C, 51.37; H, 5.23; N, 4.28.
(4R,5R,1′S)-N,O-Di(p-tolu en esu lfon yl)-5-(1′-am in oallyl)-
4-h yd r oxym eth yl-1,3-d ioxola n -2-on e (15). To a solution of
14 (310 mg, 0.93 mmol), Bu2SnO (15 mg, 0.04 mmol), and Et3N
(110 mg, 1.1 mmol) in dry CH2Cl2 (15 mL) was added
p-toluenesulfonyl chloride (188 mg, 1 mmol), and then the
mixture was stirred at room temperature. After the reaction
was complete as monitored with TLC, the mixture was
evaporated under vacuum and purified by column chromatog-
(30) Kimura, M.; Tanaka, S.; Tamaru, Y.; J . Org. Chem. 1995, 60,
3764.