1220 J . Org. Chem., Vol. 62, No. 5, 1997
McDonald et al.
pylammonium perruthenate (TPAP) (0.36 g, 1.0 mmol) was
added in one portion. The reaction mixture was warmed to
room temperature and stirred for 2 h. The reaction was
monitored to completion by TLC, and the mixture was filtered
through a short pad of silica with CH2Cl2. The filtrate was
evaporated, and the residual dialdehyde was diluted with THF
(40 mL) and stirred under nitrogen. In a separate dry three-
neck flask was stirred NaH (60% oil dispersion) (1.81 g, 45.3
mmol) in THF (60 mL). The NaH suspension was cooled to 0
°C, triethyl phosphonoacetate (8.90 mL, 45.3 mmol) was added
dropwise, and the solution was allowed to stir for 5 min. The
suspension of activated triethyl phosphonoacetate was added
in one portion to the dialdehyde. Analysis by TLC indicated
that the reaction was complete in less than 5 min. The
reaction was immediately quenched with NH4Cl (100 mL), and
the aqueous layer was extracted with ethyl acetate (2 × 50
mL). The combined organic layers were washed with water
and brine, dried with MgSO4, filtered, and concentrated.
Chromatography on silica (3:1 hexane:EtOAc) and subsequent
recrystallization yielded 2.2 g (58%) of 6 as a white solid: mp
(1R,3S,4S,6S,7S,9R)-1,9-Bis(h yd r oxym et h yl)t er cyclo-
p r op a n e (9). To a solution of Et2Zn (4.53 mL, 4.5 mmol, 1.0
M in hexanes) in 75 mL of dry CH2Cl2 at -5 °C was added
CH2I2 (0.73 mL, 9.1 mmol) at a rate of 0.2 mL/min. After the
mixture was stirred for an additional 5 min, 35 mL of an
anhydrous CH2Cl2 solution which contained the D-tartrate-
derived dioxaboralane 11 (0.49 g, 1.8 mmol) and the bis(allylic
alcohol) 7 (65 mg, 0.82 mmol) was added in one portion. The
resulting mixture was stirred at room temperature for 2 h.
Saturated aqueous NH4Cl (50 mL) was added, and the product
was extracted with Et2O. The organic extract was stirred over
5 N KOH for 2 h, dried over MgSO4, and concentrated under
reduced pressure. Purification of the oil by chromatography
on silica using ethyl acetate as the eluent yielded 42 mg (65%
yield) of 9 as a clear oil: [R]25 ) +113.2 (c 0.042, CHCl3); 1H
D
NMR (CDCl3) δ 3.39 (d, J ) 6.9 Hz, 4H), 1.90 (s, 2H), 0.84 (m,
2H), 0.70 (m, 2H), 0.57 (m, 2H), 0.29 (m, 4H), 0.15 (dd, J )
4.9 Hz, 2H); 13C (CDCl3) δ 66.93, 19.70, 18.55, 18.17, 9.22, 8.58
(major isomer); CIMS (NH3) m/e 165, 147, 133, 123, 105, 99;
HRMS (CI-NH3) calcd for C11H22O2N (M + NH4+) 200.1650,
obsd 200.1646.
) 73-74 °C; [R]25 ) +298 (c 3.7, CHCl3); 1H NMR (CDCl3) δ
D
6.45 (dd, J ) 15.6, 9.3 Hz, 2H), 5.90 (d, J ) 15.6 Hz, 2H), 4.15
(q, J ) 7.1 Hz, 4H), 1.85 (m, 2H), 1.25 (m, 8H); 13C NMR
(CDCl3) δ 166.3, 149.5, 119.9, 60.2, 25.1, 19.0, 14.3. Anal.
Calcd for C13H18O4: C, 65.53; H, 7.61. Found: C, 65.16; H,
7.45.
(+)-(1R,2S)-1-[(2-Eth oxyca r bon yl)eth en yl]-2-[(tr ip h e-
n ylm eth oxy)m eth yl]cyclop r op a n e (16). A dry three-neck
round-bottom flask was charged with CH2Cl2 (100 mL), oven-
dried molecular sieves (30 g), 14 (4.6 g, 14 mmol), and NMO
(1.74 g, 15 mmol). The solution was cooled to 0 °C, and a
catalytic amount of TPAP (0.24 g, 0.67 mmol) was added. The
reaction mixture was stirred at room temperature for 2 h. The
reaction mixture was filtered through a short pad of silica with
CH2Cl2. The filtrate was evaporated, and the residual alde-
hyde was diluted with THF (50 mL) and stirred under
nitrogen. In a separate dry three-neck flask equipped with a
septum and nitrogen inlet was stirred NaH (0.89 g, 15 mmol,
60% dispersion) in 50 mL of THF. The suspension was cooled
to 0 °C, triethyl phosphonoacetate (2.94 mL, 15 mmol) was
added dropwise, and the solution was allowed to stir for 5 min.
The suspension of activated triethyl phosphonoacetate was
added in one portion to the aldehyde. Analysis by TLC
indicated that the reaction was complete within 5 min. The
reaction was immediately quenched with saturated aqueous
NH4Cl (50 mL), and the aqueous layer was extracted with
EtOAc (2 × 100 mL). The combined organic solutions were
washed successively with water and brine, dried with MgSO4,
filtered, and concentrated. Chromatography on silica (3:1
Byp r od u ct fr om th e Cou p led TP AP Oxid a tion /Hor -
n er -Em m on s Rea ction on Com p ou n d 5. A minor product
(<10%) was isolated from the reaction mixture and was
identified as 15: 1H NMR (CDCl3) δ 6.43 (m, 2H), 5.96 (d, J )
15.4 Hz, 1H), 5.88 (d, J ) 15.4 Hz, 1H), 4.18 (q, J ) 7.1 Hz,
4H), 4.05 (m, 1H), 3.94 (m, 1H), 2.13 (m, 1H), 1.85 (m, 1H),
1.54 (m, 2H), 1.43 (m, 1H), 1.28 (dd, J ) 7.0 Hz, 6H), 1.17 (m,
1H), 0.94 (m, 2H); 13C NMR (CDCl3) δ 172.6, 166.6, 166.3,
151.1, 148.4, 121.3, 119.4, 67.5, 60.5, 60.3, 24.6, 22.9, 21.0, 20.5,
16.7, 14.4, 13.6; EIMS m/z 336 (M+), 152, 95, 79, 29.
(+)-(1S,2S)-tr a n s-1,2-Bis[(E)-3-h yd r oxyp r op en yl]cyclo-
p r op a n e (7). In a dry three-neck flask equipped with a
septum and nitrogen inlet was stirred a solution of the diester
6 (1.6 g, 6.8 mmol) in THF (100 mL). The solution was cooled
to 0 °C, and DIBAL-H (22.5 mL, 26.5 mmol, 1.5 M in toluene)
was added. The reaction mixture was stirred at room tem-
perature for 2 h. Celite was added to the reaction mixture in
order to aid filtration, and the mixture was quenched by
sequential addition of H2O (5 mL), 2 N NaOH (10 mL), and
H2O (5 mL). The resulting salts were removed by filtration
through Celite, and the solvent was removed under reduced
pressure. Chromatography on silica was performed with ethyl
acetate as the eluent and yielded 722 mg (69% yield) of 7 as a
clear oil: [R]25D ) +220 (c 0.20, CHCl3); 1H (CDCl3) δ 5.71 (dt,
J ) 15.3, 6.1 Hz, 2H), 5.28 (dd, J ) 15.3, 8.4 Hz, 2H), 4.08 (m,
4H), 1.45 (m, 2H), 1.32 (m, 2H), 0.87 (m, 2H); 13C NMR (CDCl3)
δ 135.1, 127.6, 63.8, 23.5, 15.3; CI-MS m/e 154, 137, 119, 109,
93; HRMS (CI-NH3) calcd for C9H18O2N (M + NH4+) 172.1338,
obsd 172.1345.
hexane:EtOAc) afforded 4.15 g (75% yield) of 16 as a colorless
1
semisolid: [R]25 ) +88 (c 0.40, CHCl3); H NMR (CDCl3) δ
D
7.44 (m, 6H), 7.27 (m, 9H), 6.50 (dd, J ) 15.4, 9.9 Hz, 1H),
5.85 (d, J ) 15.4 Hz, 1H), 4.17 (q, J ) 7.1 Hz, 2H), 3.03 (m,
2H), 1.44 (m, 1H), 1.39 (m, 1H), 1.29 (t, J ) 7.1 Hz, 3H), 0.86
(m, 2H); 13C NMR (CDCl3) δ 166.7, 152.5, 144.1, 128.6, 127.7,
126.9, 118.4, 86.4, 65.9, 60.0, 22.5, 20.0, 14.3, 13.5; MS (FAB)
m/e 413, 387, 271, 255, 243, 176, 165; HRMS (FAB-MNa+)
calcd for C28H29O3 (M + H+) 413.2117, obsd 413.2105. Anal.
Calcd for C28H28O3: C, 81.52; H, 6.84. Found: C, 81.21; H,
7.11.
(+)-(1R,2S)-1-[(E)-3-H yd r oxyp r op en yl]-2-[(t r ip h en yl-
m et h oxy)m et h yl]cyclop r op a n e (17). A dried three-neck
flask was charged with THF (50 mL) and ester 16 (4.05 g, 10
mmol). The solution was cooled in an ice bath, DIBAL-H
(13.76 mL, 21 mmol, 1.5 M in hexane) was added slowly, and
the solution was allowed to stir at room temperature for 4 h.
The reaction mixture was quenched by sequential addition of
H2O (0.5 mL), 2 N NaOH (1.0 mL), and H2O (0.5 mL). The
inorganic salts were removed by filtration through Celite. The
resulting filtrate was concentrated under reduced pressure,
and the resultant oil was purified by chromatography on silica
(3:1 hexane:EtOAc) to afford 2.5 g (70% yield) of 17 as a
(1S,3R,4S,6S,7R,9S)-1,9-Bis(h yd r oxym et h yl)t er cyclo-
p r op a n e (4). To a solution of Et2Zn (23.4 mL, 23.4 mmol,
1.0 M in hexanes) in 500 mL of dry CH2Cl2 at -5 °C was added
CH2I2 (3.8 mL, 46.8 mmol) at a rate of 0.2 mL/min. The
solution was stirred at -5 °C, and an anhydrous CH2Cl2
solution (50 mL) which contains the L-tartrate-derived diox-
aboralane 10 (2.8 g, 10.3 mmol) and the bis(allylic alcohol) 7
(0.72 g, 4.7 mmol) was added in one portion. The resulting
mixture was stirred at room temperature for 2 h. Saturated
aqueous NH4Cl (250 mL) was added, and the product was
extracted with Et2O. The organic extract was stirred over 5
N KOH for 2 h, dried over MgSO4, concentrated under reduced
pressure, and purified by flash chromatography on silica using
colorless oil: [R]25 ) +47.2 (c 0.57, CHCl3); 1H NMR (CDCl3)
D
ethyl acetate as the eluent to yield 708 mg (83% yield) of 4 as
δ 7.44 (m, 6H), 7.27 (m, 9H), 5.69 (dt, J ) 15.3, 6.1 Hz, 1H),
5.31 (dd, J ) 15.3, 8.7 Hz, 1H), 4.10 (m, 2H), 3.02 (m, 1H),
2.97 (m, 1H), 1.55 (s, 1H), 1.24 (m, 1H), 1.15 (m, 1H), 0.65 (m,
2H); 13C NMR (CDCl3) δ 153.2, 144.3, 135.9, 128.6, 127.7,
126.9, 86.2, 66.6, 63.6, 20.6, 19.1, 11.9; MS (FAB) m/e 293, 259,
243, 215, 183, 165; HRMS (FAB-MNa+) calcd for C26H22O2Na
(M + Na+) 393.1830, obsd 393.1833.
1
a clear oil: [R]25 ) +191.7 (c 0.65, CHCl3); H NMR (CDCl3)
D
δ 3.40 (d, J ) 6.8 Hz, 4H), 1.49 (s, 2H), 0.83 (m, 2H), 0.72 (m,
2H), 0.60 (m, 2H), 0.28 (m, 4H), 0.15 (dd, J ) 6.8 Hz, 2H); 13
C
NMR (CDCl3) δ 66.98, 19.88, 18.48, 18.38, 8.45, 8.32; CIMS
(NH3) m/e 165, 147, 133, 123; HRMS (CI-NH3) calcd for
C11H22O2N (M + NH4+) 200.1650, obsd 200.1659.