Swain et al.
1
νmax 1736, 1504 cm-1; H NMR (400 MHz) δ 7.27 (1H, d, J )
enzyme was then filtered, washed with EtOAc (30 mL), and
the filtrate concentrated in vacuo to yield a colorless oil (790
mg). Purification was accomplished by flash chromatography
on silica gel (3.2 × 14) eluting with EtOAc/hexane (1:1 then
2:1 then 3:1) to give the title compound 36b (247 mg, 0.43
mmol, 72%) as a white foamy solid: mp 57-59 °C; [R]D +31.2
(c 0.38, CHCl3); IR νmax (neat) 1771, 1718 cm-1; 1H NMR (400
MHz) δ 7.30-7.25 (2H, m), 6.94-6.91 (2H, m), 6.89 (1H, dd, J
) 8.3, 1.8 Hz), 6.76 (1H, dd, J ) 8.3, 1.8 Hz), 5.26 (1H, d, J )
9.0 Hz), 4.53 (1H, d, J ) 12.3 Hz), 4.44 (1H, d, J ) 12.3 Hz),
3.96 (1H, d, J ) 10.0 Hz), 3.89 (3H, s), 3.85 (3H, s), 3.55 (2H,
d, J ) 3.8 Hz), 3.20 (3H, s), 3.18 (3H, s), 3.13 (1H, ddt, J )
10.0, 9.0, 3.8 Hz), 2.50 (3H, s); keto/enol ratio 12:1, enolic
resonances were observed at δ 11.24 (1H, s), 5.49 (1H, d, J )
2.5 Hz), 4.58 (1H, d, J ) 10.0 Hz), 1.96 (3H, s); 13C NMR (100
MHz) δ 200.4, 171.3, 152.5, 152.1, 139.1, 138.3, 138.3, 125.2,
125.1, 120.6, 119.4, 112.7, 110.7, 81.0, 73.2, 67.0, 56.7, 56.6,
56.3, 46.3, 39.0, 38.9, 30.5; enolic resonances were observed
at δ 141.4, 117.8, 19.8; LRMS (ES +ve) m/z (relative intensity)
595 (100) [M + Na]+. Anal. Calcd for C24H28S2O12: C, 50.34;
H, 4.93. Found: C, 50.19; H, 5.01.
(4R,5S)-5-(4-Meth a n esu lfon yloxy-3-m eth oxy)p h en yl-3-
d ia zo-4-{[(4-m eth a n esu lfon yloxy-3-m eth oxyben zyl)oxy]-
m eth yl}tetr a h yd r o-2-fu r a n on e (37b). The title compound
was prepared according to the method outlined for 23, whereby
reaction of lactone 36b (160 mg, 0.28 mmol) with Tf2O (0.19
mL, 1.12 mmol) and NaN3 (146 mg, 2.24 mmol) and workup
under the conditions described gave a crude yellow oil (226
mg). Purification was accomplished by flash chromatography
on silica gel (2.2 × 9) eluting with EtOAc/hexane (3:1) to give
the title compound 37b (150 mg, 0.27 mmol, 96%) as a viscous
bright yellow foam: [R]D +42.3 (c 0.41, CHCl3); IR νmax (neat)
2101, 1731, 1603 cm-1; 1H NMR (400 MHz) δ 7.30 (1H, d, J )
8.3 Hz), 7.27 (1H, d, J ) 8.3 Hz), 6.97 (1H, d, J ) 2.0 Hz),
6.96 (1H, d, J ) 2.0 Hz), 6.89 (1H, d, J ) 1.8 Hz), 6.87 (1H, d,
J ) 1.8 Hz), 5.18 (1H, d, J ) 4.8 Hz), 4.58 (2H, s), 3.88 (3H,
s), 3.87 (3H, s), 3.85-3.71 (3H, m), 3.19 (3H, s), 3.19 (3H, s);
13C NMR (100 MHz) δ 169.2, 152.5, 152.2, 139.7, 138.9, 138.4,
138.1, 125.5, 125.0, 120.4, 118.2, 112.3, 110.2, 80.1, 73.5, 71.3,
56.7, 56.5, 53.0, 45.7, 39.0, 38.9.
8.5 Hz), 6.99-6.94 (2H, m), 6.23 (1H, d, J ) 6.0 Hz), 5.97 (1H,
ddd, J ) 17.1, 10.3, 5.8 Hz), 5.31 (1H, dt, J ) 17.1, 1.3 Hz),
5.27 (1H, dt, J ) 10.3, 1.3 Hz), 3.89 (3H, s), 3.17 (3H, s), 2.12
(3H, s); 13C NMR (100 MHz) δ 170.3, 151.9, 139.8, 138.5, 136.1,
125.0, 120.3, 117.9, 112.4, 76.0, 56.5, 38.8, 21.6; LRMS (CI,
NH3) m/z (relative intensity) 241 (60) [M + H(-CH3CO2H)]+,
260 (100); HRMS (ES +ve) calcd for C13H16SO6Na 323.0560,
found 323.0564.
(1S)-(4-Meth an esu lfon yloxy-3-m eth oxyph en yl)allyl Ac-
etoa ceta te (34). The title compound was prepared according
to the method outlined for 11 whereby (1S)-(4-methanesulfo-
nyloxy-3-methoxyphenyl)prop-2-en-1-ol ((S)-31) (5.94 g, 23
mmol) and 2,2,6-trimethyl-4H-1,3-dioxin-4-one (3.0 mL, 23.2
mmol) were reacted under the conditions described (except
reaction for 15 min). Purification was accomplished by flash
chromatography on silica gel (8 × 7) eluting with petrol (800
mL), followed by EtOAc/hexane (1:1) to give the title compound
34 (7.25 g, 21.2 mmol, 92%) as a pale yellow oil: [R]D -38.2 (c
0.34, CHCl3); IR νmax (neat) 1737, 1714, 1504 cm-1; H NMR
1
(400 MHz) δ 7.28 (1H, d, J ) 8.3 Hz), 7.02 (1H, d, J ) 2.0 Hz),
6.95 (1H, ddd, J ) 8.3, 2.0, 0.5 Hz), 6.28 (1H, d, J ) 6.0 Hz),
5.97 (1H, ddd, J ) 17.1, 10.5, 6.0 Hz), 5.36 (1H, dt, J ) 17.3,
1.3 Hz), 5.31 (1H, dt, J ) 10.3, 1.3 Hz), 3.91 (3H, s), 3.53 (2H,
s), 3.17 (3H, s), 2.25 (3H, s); keto/enol ratio 6:1, enolic
acetoacetyl resonances were observed at δ 11.90 (1H, d, J )
0.8 Hz), 5.08 (1H, d, J ) 0.8 Hz), 3.89 (3H, s), 1.97 (3H, s); 13
C
NMR (100 MHz) δ 200.6, 166.4, 152.0, 139.2, 138.5, 135.5,
125.0, 120.1, 118.7, 112.2, 77.0, 56.6, 50.6, 38.8, 30.7; enolic
acetoacetyl resonances were observed at δ 177.0, 139.8, 136.2,
117.9, 112.1, 90.0, 75.4, 21.7; LRMS (ES +ve) m/z (relative
intensity) 365 (100) [M + Na]+, 707 (30) [2M + Na]+; HRMS
(ES +ve) calcd for C15H18SO7Na 365.0665, found 365.0675.
(1R,4S,5S)-1-Acet yl-4-(4-m et h a n esu lfon yloxy-3-m et h -
oxyp h en yl)-3-oxa bicyclo[3.1.0]h exa n -2-on e (35). The title
compound was prepared according to the method outlined
above for the preparation of 12, whereby â-ketoester 34 (6.85
g, 20.0 mmol), Mn(OAc)3‚2H2O (16.1 g, 60.0 mmol), Cu(OAc)2
(5.45 g, 30.0 mmol), and KOAc (22.1 g, 225 mmol) were reacted
and worked up under the conditions described to yield a crude
yellow oil (7.38 g). Purification was accomplished by flash
chromatography on silica gel (5 × 12) eluting with EtOAc/
hexane (2:3) to give the title compound 35 (4.59 g, 13.5 mmol,
67%) as a pale yellow oil (25:1 mixture of diastereoisomers).
A series of triturations with ice-cold Et2O/hexane provided the
trans-isomer as an off-white solid: mp 113-115 °C (EtOAc/
hexane); [R]D +96.6 (c 0.38, CHCl3); IR νmax (neat) 1770, 1695,
(1S,2R,5R,6S)-2-(4-Met h a n esu lfon yloxy-3-m et h oxy)-
p h en yl-6-(4-m eth a n esu lfon yloxy-3-m eth oxy)p h en yl-3,7-
d ioxa bicyclo[3.3.0]octa n -8-on e (38b). The title compound
was prepared according to the method outlined for 27, whereby
reaction of diazolactone 37b (128 mg, 0.23 mmol) with Rh2-
(OAc)4 (2 mg, cat.) and workup under the conditions described
gave crude furofuranone as a white foam (118 mg). Purification
was accomplished by flash chromatography on silica gel (2.2
× 7) eluting with EtOAc/hexane (4:1) then EtOAc to give the
title compound 38b (97 mg, 0.18 mmol, 80%) as a white
powdery solid: mp 135-137 °C (EtOAc/hexane); [R]D +81.8 (c
1599 cm-1 1H NMR (400 MHz) δ 7.33 (1H, d, J ) 8.8 Hz),
;
6.93-6.89 (2H, m), 5.30 (1H, s), 3.90 (3H, s), 3.19 (3H, s), 2.82
(1H, dd, J ) 8.0, 6.0 Hz), 2.58 (3H, s), 2.15 (1H, dd, J ) 8.0,
4.3), 1.61 (1H, m); 13C NMR (100 MHz) δ 200.1, 172.5, 152.5,
139.4, 139.1, 125.7, 118.0, 110.3, 78.9, 56.6, 39.0, 37.2, 36.7,
29.7, 24.7; LRMS (ES +ve) m/z (relative intensity) 703 (100)
[2M + Na]+. CHN Anal. Calcd for C15H16SO7: C, 52.94; H, 4.74.
Found: C, 52.93; H, 4.78.
0.38, CHCl3); IR (neat) νmax 1779, 1602 cm-1 1H NMR (400
;
MHz) δ 7.32 (2H, d, J ) 8.3 Hz), 7.04 (1H, d, J ) 1.2 Hz), 7.01
(1H, dd, J ) 8.3, 1.5 Hz), 6.97 (1H, d, J ) 1.2 Hz), 6.91 (1H,
dd, J ) 8.3, 1.5 Hz), 5.27 (1H, d, J ) 6.3 Hz), 5.08 (1H, d, J )
8.3 Hz), 4.37 (1H, d, J ) 9.8 Hz), 3.98 (1H, dd, J ) 9.8, 4.8
Hz), 3.90 (3H, s), 3.90 (3H, s), 3.60 (1H, t, J ) 8.8 Hz), 3.26
(1H, ddd, J ) 8.8, 6.3, 4.8 Hz), 3.20 (3H, s), 3.14 (3H, s); 13C
NMR (100 MHz) δ 174.2, 152.5, 152.0, 140.4, 138.8, 138.7,
136.8, 125.5, 124.9, 119.5, 118.1, 111.4, 110.2, 85.0, 83.6, 72.7,
56.7, 56.6, 51.6, 51.3, 39.0, 38.5; LRMS (ES +ve) m/z (relative
(4R,5S)-5-(4-Meth a n esu lfon yloxy-3-m eth oxy)p h en yl-4-
{[(4-m eth a n esu lfon yloxy-3-m eth oxyben zyl)oxy]m eth yl}-
3-a cet ylt et r a h yd r o-2-fu r a n on e (36b ). To a mixture of
cyclopropane 35 (204 mg, 0.60 mmol), 4-methanesulfonyloxy-
3-methoxybenzyl alcohol (39b) (418 mg, 1.80 mmol), and 2,6-
di-tert-butylpyridine (13 µL, 0.06 mmol) was added Mg(ClO4)2
(13 mg, 0.06 mmol) and the mixture heated to 120 °C for 2.5
h. The reaction mixture was allowed to cool to room temper-
ature, diluted with CH2Cl2 (30 mL), and treated with saturated
NH4Cl(aq) (25 mL). The organic layer was separated and the
aqueous layer extracted with CH2Cl2 (3 × 30 mL). The
combined organic layers were washed with brine (30 mL),
dried with Na2SO4, and concentrated in vacuo to yield a crude
yellow oil (730 mg). To a solution of this crude material in
isopropenyl acetate (3 mL) was added Novozym 435 (140 mg,
50 wt % based on 1.2 mmol of excess alcohol 40 remaining)
and the gently stirred mixture warmed to 40 °C for 12 h. The
intensity) 1079 (100) [2M + Na]+. Anal. Calcd for C22H24S2O11
C, 49.99; H, 4.58. Found: C, 49.81; H, 4.59.
:
(2R,3R,4S)-2[(4-Meth a n esu lfon yloxy-3-m eth oxy)p h en -
y l]-3-h y d r o x y m e t h y l-4-{[(4-m e t h a n e s u lfo n y lo x y -3-
m eth oxy)p h en yl]h yd r oxy}m eth yltetr a h yd r ofu r a n (40b).
To a suspension of LiAlH4 (84 mg, 2.21 mmol) in THF (17 mL)
at 0 °C (ice bath) was added a solution of furofuranone 38b
(390 mg, 0.74 mmol) in THF (25 mL) dropwise over 10 min
and the gray suspension stirred for a further 10 min. Water
(0.12 mL), 15% NaOH(aq) (0.12 mL), and water (0.36 mL) were
sequentially added dropwise to the reaction mixture at 0 °C,
128 J . Org. Chem., Vol. 69, No. 1, 2004