Polyhydroxylated 1-Vinylcycloalkenes by Methathesis from Carbohydrate-Derived Enynes
FULL PAPER
10.4, J6Ϫ7b ϭ 18.1 Hz, 6-H), 5.41 (br. dd, J7a-7b ϭ 1.8 Hz, 7a-H), 3 from 14 (100 mg, 0.2 mmol). The crude residue was purified by
5.33 (ddd, J5Ϫ7b ϭ 0.8 Hz, 7b-H), 5.00, 4.95, 4.88, 4.69, 4.59, 4.53 flash chromatography (hexane/EtOAc, 97:3) and 21 was obtained
(dd, J1Ϫ3 ϭ 2.1, J3Ϫ4 ϭ 5.2 Hz, 3-H), 4.46 (d, PhCH2), 4.15 (br. as a colorless oil in 66% yield (66 mg). Rf ϭ 0.30 (hexane/EtOAc,
ddd, 5-H), 3.95 (t, J4Ϫ5 ϭ 5.2 Hz, 4-H), 2.10 (d, 1-H) ppm. 13C 9:1). [α]D26 ϭ Ϫ30 (c ϭ 0.63, CHCl3). IR (CHCl3): ν˜ ϭ 1641 cmϪ1
NMR (CDCl3): δ ϭ 139.0Ϫ128.2 (C6H5), 135.6 (C-6), 120.1 (C-7), 1H NMR (CDCl3): δ ϭ 7.40Ϫ7.30 (m, C6H5), 6.33 (dd, J1Ј-2Јa
.
ϭ
82.5 (C-4), 81.0 (C-2, C-5), 75.8 (C-1), 75.1, 71.4, 71.5 (PhCH2),
70.8 (C-3) ppm. C28H28O3: calcd. C 81.52, H 6.84; found C 81.83,
H 6.56. MS: m/z ϭ 435.2 [M ϩ Na]ϩ.
11.1, J1Ј-2Јb ϭ 17.6 Hz, 1Ј-H), 6.00 (d, J2Ϫ3 ϭ 5.6 Hz, 2-H), 5.64
(dd, J2Јa-2Јb ϭ 0.7 Hz, 2Јb-H), 5.22 (dd, 2Јa-H), 5.02, 4.89, 4.78,
4.57, 4.57 (d, J5Ϫ6 ϭ 7.1 Hz, 6-H), 4.55 (d, PhCH2), 4.50 (dd,
J4Ϫ5 ϭ 9.5 Hz, 5-H), 4.18 (dd, J3Ϫ4 ϭ 3.4 Hz, 3-H), 3.62 (dd, 4-
H) ppm. 13C NMR (CDCl3): δ ϭ 140.2 (C-1), 139.3Ϫ128.0 (C6H5),
135.9 (C-1Ј), 127.3 (C-2), 117.2 (C-2Ј), 79.9 (C-6), 79.8 (C-4), 78.7
(C-5), 74.9, 72.9, 72.0, 71.3 (C-3), 69.2 (PhCH2) ppm. C36H36O4:
calcd. C 81.17, H 6.81; found C 81.42, H 6.72. MS: m/z ϭ 555.2
[M ϩ Na]ϩ.
(4S,5R)-4,5-Di-O-benzylhept-6-en-1-yne-4,5-diol (18): The com-
pound 18 was prepared by general procedure 2 from 12 (595 mg,
1.92 mmol). The crude residue was purified by flash chromatogra-
phy (hexane/EtOAc, 99:1) and 18 was obtained as a colorless oil in
64% yield (375 mg). Rf ϭ 0.55 (hexane/EtOAc, 9:1). [α]2D5 ϭ Ϫ34
(c ϭ 0.9, CHCl3). IR (CHCl3): ν˜ ϭ 2223, 1642 cmϪ1 1H NMR
.
(CDCl3): δ ϭ 7.40Ϫ7.30 (m, C6H5), 6.02 (ddd, J5Ϫ6 ϭ 5.5, J6Ϫ7a ϭ
9.5, J6Ϫ7b ϭ 18.0 Hz, 6-H), 5.53 (m, J7a-7b ϭ 0.84 Hz, 7a-H), 5.48
(ddd, 7b-H), 4.84, 4.83, 4.79, 4.54 (d, PhCH2), 4.13 (tt, J4Ϫ5 ϭ 5.5,
J5Ϫ7a ϭ J5Ϫ7b ϭ 1.0 Hz, 5-H), 3.82 (q, J3a-4 ϭ J3b-4 ϭ 5.5 Hz, 4-
H), 2.66 (m, 3a-H, 3b-H), 2.11 (t, J1Ϫ3a ϭ J1Ϫ3b ϭ 2.7 Hz, 1-H)
ppm. 13C NMR (CDCl3): δ ϭ 138.9Ϫ128.0 (C6H5), 135.8 (C-6),
120.0 (C-7), 82.0 (C-5), 81.8 (C-2), 79.9 (C-4), 73.3, 71.2 (PhCH2),
70.5 (C-1), 21.7 (C-3) ppm. C21H22O2: calcd. C 83.32, H 7.24;
found C 83.49, H 7.02. MS: m/z ϭ 329.4 [M ϩ Na]ϩ.
(3R,4R,5R,6R)-3,4,5,6-Tetra-O-benzyl-1-vinylcyclohexene-3,4,5,6-
tetrol (22): The compound 22 was prepared by general procedure
3 from 15 (130 mg, 0.25 mmol). The crude residue was purified by
flash chromatography (hexane/EtOAc, 97:3) and 22 was obtained
as a colorless oil in 55% yield (74 mg). Rf ϭ 0.35 (hexane/EtOAc,
9:1). [α]2D8 ϭ Ϫ107 (c ϭ 0.4, CHCl3). IR (CHCl3): ν˜ ϭ 1641 cmϪ1
.
ϭ
1H NMR (CDCl3): δ ϭ 7.40Ϫ7.30 (m, C6H5), 6.32 (dd, J1Ј-2Јa
11.0, J1Ј-2Јb ϭ 17.6 Hz, 1Ј-H), 5.83 (d, J2Ϫ3 ϭ 4.2 Hz, 2-H), 5.33
(d, 2Јb-H), 5.17 (d, 2Јa-H), 5.11, 5.01, 4.90, 4.86, 4.82, 4.73, 4.70,
4.68 (d, PhCH2), 4.55 (d, J5Ϫ6 ϭ 3.2 Hz, 6-H), 4.27 (dd, J4Ϫ5
ϭ
General Procedure 3 for Enyne Metathesis 19؊25: Freshly distilled
CH2Cl2 was degassed for 1 h. The enyne (0.5 mmol) was dissolved
in CH2Cl2 (8 mL) and ethylene gas was passed through the solution
for 45 min. Ruthenium catalyst B (15% mol) or A (30% mol) in
CH2Cl2 (2 mL) was then added, and the solution was degassed
again with ethylene for 20 min. The mixture was stirred under an
atmosphere of ethylene at room temperature. The reaction was
monitored by TLC. The mixture was then concentrated and the
residue was purified by flash chromatography.
9.0 Hz, 5-H), 4.26 (t, J3Ϫ4 ϭ 4.2 Hz, 3-H), 4.17 (dd, 4-H) ppm. 13
C
NMR (CDCl3): δ ϭ 139.4Ϫ127.0 (C6H5), 138.4 (C-1), 137.0 (C-
1Ј), 128.0 (C-2), 115.4 (C-2Ј), 78.7 (C-4), 76.9 (C-3), 74.7, 74.2 (C-
6), 74.1, 73.7, 73.5 (C-5), 73.2 (PhCH2) ppm. C36H36O4: calcd. C
81.17, H 6.81; found C 81.35, H 6.66. MS: m/z ϭ 555.2 [M ϩ Na]ϩ.
(3R,4S,5R,6S)-3,4,5,6-Tetra-O-benzyl-1-vinylcyclohexene-3,4,5,6-
tetrol (23): The compound 23 was prepared by general procedure
3 from 16 (25 mg, 4.7·10Ϫ5 mol). The crude residue was purified
by flash chromatography (hexane/EtOAc, 97:3) and 23 was ob-
tained as a colorless oil in 68% yield (17 mg). Rf ϭ 0.34 (hexane/
EtOAc, 9:1). [α]2D3 ϭ ϩ10 (c ϭ 0.15, CHCl3). IR (CHCl3): ν˜ ϭ 1645
(3R,4S,5R)-3,4,5-Tri-O-benzyl-1-vinylcyclohexene-3,4,5-triol (19):
The compound 19 was prepared by general procedure 3 from 13
(210 mg, 0.49 mmol). The crude residue was purified by flash chro-
matography (hexane/EtOAc, 98:2) and 19 was obtained as a color-
cmϪ1 1H NMR (CDCl3): δ ϭ 7.40Ϫ7.30 (m, C6H5), 6.32 (dd,
.
J1Ј-2Јa ϭ 11.0, J1Ј-2Јb ϭ 17.7 Hz, 1Ј-H), 5.94 (d, J2Ϫ3 ϭ 2.6 Hz, 2-
H), 5.16 (br. d, 2Јb-H), 5.02 (br. d, 2Јa-H), 4.81, 4.70, 4.67, 4.55,
less oil in 72% yield (200 mg). Rf ϭ 0.36 (hexane/EtOAc, 9:1). [α]
27
ϭ Ϫ96 (c ϭ 0.57, CHCl3). IR (CHCl3): ν˜ ϭ 1641 cmϪ1 1H
.
D
NMR (CDCl3): δ ϭ 7.40Ϫ7.30 (m, C6H5), 6.41 (dd, J2Јa-1Ј ϭ 17.4,
J2Јb-1Ј ϭ 10.8 Hz, 1-HЈ), 5.80 (d, J2Ϫ3 ϭ 4.1 Hz, 2-H), 5.24 (d, 2Јa-
H), 5.12 (d, 2Јb-H), 4.78, 4.74, 4.71 (d, PhCH2), 4.30 (t, J3Ϫ4 ϭ 3.9
Hz, 3-H), 4.18 (m, J4Ϫ5 ϭ 8.2, J5Ϫ6a ϭ 5.5, J5Ϫ6b ϭ 5.7 Hz, 5-H),
3.80 (dd, 4-H), 2.77 (dd, J6a-6b ϭ 17.4 Hz, 6a-H), 2.28 (dd, 6b-H)
ppm. 13C NMR (CDCl3): δ ϭ 138.9 (C-1Ј), 139.3Ϫ128.1 (C6H5),
136.9 (C-1), 126.5 (C-2), 114.2 (C-2Ј), 79.1 (C-4), 74.8 (C-5), 73.3
(C-3), 73.2, 72.9, 72.2 (PhCH2), 30.0 (C-6) ppm. C29H30O3: calcd.
C 81.66, H 7.09; found C 81.89, H 6.91. MS: m/z ϭ 449.2 [M
ϩ Na]ϩ.
4.50 (dd, J3Ϫ4 ϭ 9.5 Hz, 3-H), 4.47 (d, PhCH2), 4.17 (d, J5Ϫ6
ϭ
5.9 Hz, 6-H), 4.00 (m, 4-H, 5-H) ppm. 13C NMR (CDCl3): δ ϭ
139.3Ϫ128.0 (C6H5), 138.5 (C-1), 137.1 (C-1Ј), 131.3 (C-2), 114.6
(C-2Ј), 78.9, , 76.9 (C-3), 75.0 (C-4, C-5), 75.0 (C-6), 73.3, 72.9,
72.5 (PhCH2) ppm. C36H36O4: calcd. C 81.17, H 6.81; found C
81.40, H 6.62. MS: m/z ϭ 555.2 [M ϩ Na]ϩ.
(3R,4R,5S)-3,4,5-Tri-O-benzyl-1-vinylcyclopentene-3,4,5-triol (24):
By general procedure 3, from reaction of 17 (200 mg, 0.485 mmol),
two compounds were isolated 24 and 25 by flash chromatography
(hexane/EtOAc, 97:3). The compound 24 was obtained as a color-
1,2-Bis[(3ЈR,4ЈS,5ЈR)-3Ј,4Ј,5Ј-Tris(benzyloxy)cyclohex-1-ene-1yl]-
ethene (20): 20 was obtained as a colorless oil in 72% yield (200
mg). Rf ϭ 0.24 (hexane/EtOAc, 9:1). [α]2D6 ϭ Ϫ123 (c ϭ 0.20,
less oil in 40% yield (80 mg). Rf ϭ 0.34 (hexane/EtOAc, 9:1). [α]D27
ϭ
Ϫ57 (c ϭ 0.8, CHCl3). IR (CHCl3): ν˜ ϭ 1654 cmϪ1 1H NMR
.
(CDCl3): δ ϭ 7.40Ϫ7.30 (m, C6H5), 6.53 (dd, J1Ј-2Јa ϭ 17.7, J1Ј-
2Јb ϭ 10.9 Hz, 1Ј-H), 6.06 (d, J2Ϫ3 ϭ 2.4 Hz, 2-H), 5.65 (d, 2Јa-H),
5.34 (d, 2Јb-H), 4.90, 4.87 (d, J4Ϫ5 ϭ 5.8 Hz, 5-H), 4.60 (m,
PhCH2), 4.55 (dd, J3Ϫ4 ϭ 5.8 Hz, 3-H), 4.14 (t, 4-H) ppm. 13C
NMR (CDCl3): δ ϭ 144.3 (C-1), 139.6Ϫ127.8 (C6H5), 132.0 (C-
1Ј), 131.5 (C-2), 119.1 (C-2Ј), 78.9 (C-3, C-4), 78.0 (C-5), 72.4, 72.0,
70.5 (PhCH2) ppm. C28H28O3: calcd. C 81.52, H 6.84; found C
81.49, H 6.94. MS: m/z ϭ 435.2 [M ϩ Na]ϩ.
1
CHCl3). H NMR (CDCl3): δ ϭ 7.40Ϫ7.30 (m, C6H5), 6.28 (s, 1-
H), 5.85 (d, J2Ј-3Ј ϭ 4.0 Hz, 2Ј-H), 4.78, 4.74, 4.71 (d, PhCH2), 4.32
(t, J3Ј-4Ј ϭ 3.8 Hz, 3Ј-H), 4.18 (m, J5Ј-6aЈ ϭ 5.5, J5Ј-6bЈ ϭ 5.8 Hz,
5Ј-H), 3.90 (dd, J4Ј-5Ј ϭ 9.0 Hz, 4Ј-H), 2.79 (dd, J6aЈ-6bЈ ϭ 17.4 Hz,
6aЈ-H), 2.31 (dd, 6bЈ-H) ppm. 13C NMR (CDCl3): δ ϭ 136.7 (C-
1Ј), 139.3Ϫ128.1 (C6H5), 130.7 (C-1), 126.9 (C-2Ј), 79.2 (C-4Ј), 74.8
(C-5Ј), 73.5 (C-3Ј), 73.2, 72.9, 72.2 (PhCH2), 30.1 (C-6Ј) ppm.
C56H56O6: calcd. C 81.52, H 6.84; found C 81.90, H 6.95. MS:
m/z ϭ 849.0 [M ϩ Na]ϩ.
(4R,5R,6S)-4,5,6-Tri-O-benzyl-1-methylenecyclohex-2-ene-4,5,6-
triol (25): The compound 25 was obtained as a colorless oil in 21%
yield (43 mg). Rf ϭ 0.30 (hexane/EtOAc, 9:1). [α]2D3 ϭ Ϫ22 (c ϭ
(3R,4R,5R,6S)-3,4,5,6-Tetra-O-benzyl-1-vinylcyclohexene-3,4,5,6-
tetrol (21): The compound 21 was prepared by general procedure
Eur. J. Org. Chem. 2003, 2336Ϫ2342
2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2341