The Journal of Organic Chemistry
Note
3; HRMS (ESI-TOF) m/z [M + H]+ calcd for C17H31O8 363.2019,
found 363.2015.
4.82 (2H, ABq, J = 11.5 Hz), 4.96 (1H, d, J = 4.0 Hz), 4.83 and 4.50
(2H, ABq, J = 11.0 Hz), 4.78 (1H, d, J = 4.0 Hz), 4.65 and 4.47 (2H,
ABq, J = 12.0 Hz), 4.19 (1H, m), 4.11 (1H, dd, J = 5.0, 10.0 Hz), 3.86
(1H, dd, J = 10.0, 10.0 Hz), 3.82−3.77 (3H, m), 3.74−3.63 (6H, m),
3.42 (3H, s), 2.64 (1H, br-s), 2.46 (1H, d, J = 10.0 Hz), 1.05 (9H, s),
0.99 (9H, s); 13C{1H} NMR (125 MHz, CDCl3) δ 138.8, 138.3,
137.9, 128.3 × 2, 127.9 × 2, 127.8, 127.6 × 2, 127.5, 97.3, 83.6, 77.4,
76.4, 75.3, 74.9, 73.4, 73.0, 72.1, 70.6, 68.3, 66.4, 65.6, 55.4, 27.4,
26.9, 22.7, 19.9; HRMS (ESI-TOF) m/z [M + H]+ calcd for
C42H59O11Si 767.3827, found 767.3803.
Compound 23B. To a solution of 10 (0.57 mg, 6.36 μmol) and
2312 (13.4 mg, 31.8 μmol) in dry MeCN (0.2 M, 318 μL) was added
a solution of 14 (27.5 mg, 63.6 μmol) in dry MeCN (0.2 M, 318 μL)
at room temperature under an Ar atmosphere. After the reaction
mixture was stirred for 4 h, the reaction was quenched by the addition
of 50 mM NaBO3 (aq, 7.00 μmol). The aqueous layer was extracted
with EtOAc (3 mL × 5), and then the combined extracts were washed
with sat. NH4Cl (aq, 2 mL), sat. NaHCO3 (aq, 2 mL), and brine,
dried over anhydrous Na2SO4, and concentrated in vacuo. The residue
was purified by preparative TLC (5:1 n-hexane/acetone) to afford
23B (12.3 mg, 14.3 μmol, 45% yield): colorless syrup; Rf 0.31 (5:1 n-
hexane/acetone); [α]D28 +102.9° (c 0.73, CHCl3); 1H NMR (500
MHz, CDCl3) δ 7.40−7.39 (2H, m), 7.34−7.26 (11H, m), 7.13−7.11
(2H, m), 4.99 and 4.82 (2H, ABq, J = 11.0 Hz), 4.96 (1H, d, J = 4.0
Hz), 4.82 and 4.47 (2H, ABq, J = 11.0 Hz), 4.78 (1H, d, J = 3.5 Hz),
4.61 and 4.51 (2H, ABq, J = 12.0 Hz), 4.04 (1H, m), 3.85 (1H, br-d, J
= 11.0 Hz), 3.77−3.67 (6H, m), 3.60−3.55 (2H, m), 3.51−3.49 (2H,
m), 3.38 (3H, s), 2,57 (1H, d, J = 3.5 Hz), 2.50 (1H, d, J = 10.0 Hz),
0.89 (9H, s), 0.88 (9H, s), 0.12 (3H, s), 0.09 (3H, s), 0.06 (6H, s);
13C{1H} NMR (125 MHz, CDCl3) δ 138.7, 138.0, 137.8, 128.4 × 2,
128.0, 127.9, 127.7 × 2, 127.6, 97.8, 96.7, 83.5, 78.7, 75.3, 75.1, 73.4,
73.1, 72.9, 72.3, 71.1, 71.0, 68.3, 62.4, 54.7, 25.9 × 2, 18.4, 18.3, −3.9,
−4.9, −5.1, −5.4; HRMS (ESI-TOF) m/z [M + K]+ calcd for
C46H70O11Si2K 893.4094, found 893.4112.
Compound 24A and 24B. To a solution of 10 (0.64 mg, 7.14
μmol) and 2413 (10.2 mg, 35.7 μmol) in dry MeCN (0.2 M, 357 μL)
was added a solution of 14 (30.9 mg, 71.4 μmol) in dry MeCN (0.2
M, 357 μL) at room temperature under an Ar atmosphere. After the
reaction mixture was stirred for 4 h, the reaction was quenched by the
addition of 50 mM NaBO3 (aq, 7.85 μmol). The aqueous layer was
extracted with EtOAc (3 mL × 5), and then the combined extracts
were washed with sat. NH4Cl (aq, 2 mL), sat. NaHCO3 (aq, 2 mL),
and brine, dried over anhydrous Na2SO4, and concentrated in vacuo.
The residue was purified by preparative TLC (4:1 toluene/EtOAc) to
afford 24A (9.3 mg, 13.0 μmol, 36% yield) and 24B (8.9 mg, 12.9
μmol, 36% yield).
Compound 24A: colorless syrup; Rf 0.42 (4:1 toluene/acetone);
[α]2D5 +89.3° (c 0.72, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.37−
7.27 (13H, m), 7.15−7.13 (2H, m), 5.05 (1H, dd, J = 9.6, 10.0 Hz),
4.91 (1H, d, J = 4.0 Hz), 4.90 and 4.80 (2H, ABq, J = 11.2 Hz), 4.80
(1H, d, J = 5.2 Hz), 4.80 and 4.46 (2H, ABq, J = 11.2 Hz), 4.56 and
4.49 (2H, ABq, J = 13.2 Hz), 4.28−4.21 (2H, m), 4.07 (1H, br-d, J =
12.4 Hz), 3.90−3.84 (2H, m), 3.72−3.55 (5H, m), 3.45 (1H, dd, J =
9.2, 9.6 Hz), 3.40 (3H, s), 3.24 (1H, d, J = 8.0 Hz), 2.10 (3H, s), 2.07
(3H, s), 1.93 (1H, d, J = 9.2 Hz); 13C{1H} NMR (100 MHz, CDCl3)
δ 170.7 × 2, 138.5, 138.0, 137.6, 128.4 × 2, 127.9 × 2, 127.8, 127.7,
127.6, 100.4, 99.6, 83.1, 81.8, 77.5, 75.4, 74.9, 73.5, 72.9, 71.1, 70.9,
69.3, 68.8, 67.3, 62.1, 55.5, 20.9, 20.7; HRMS (ESI-TOF) m/z [M +
Na]+ calcd for C38H46O13Na 733.2836, found 733.2801.
Compound 16α and 17α. To a solution of tetrahydroxydiboron
(10) (0.80 mg, 8.92 μmol) and 1321 (12.6 mg, 44.6 μmol) in dry
MeCN (0.2 M, 446 μL) was added a solution of 149 (38.6 mg, 89.2
μmol) in dry MeCN (0.2 M, 446 μL) at room temperature under an
Ar atmosphere. After the reaction mixture was stirred for 4 h, the
reaction was quenched by the addition of 50 mM NaBO3 (aq, 9.81
μmol). The aqueous layer was extracted with EtOAc (3 mL × 5), and
then the combined extracts were washed with sat. NH4Cl (aq, 2 mL),
sat. NaHCO3 (aq, 2 mL), and brine, dried over anhydrous Na2SO4,
and concentrated in vacuo. Purification of the residue by silica gel
column chromatography (1:1 n-hexane/EtOAc) gave a mixture of
16α and 17α (29.7 mg, 41.5 μmol, 93% yield, α(1,3)/α(1,2) = 2.5:1)
as an inseparable mixture.22 Compound 16α: white solid; mp 164−
165 °C; Rf 0.35 (1:1 n-hexane/EtOAc); [α]2D7 +76.4° (c 0.76,
1
CHCl3); H NMR (400 MHz, CDCl3) δ 7.47−7.45 (2H, m), 7.39−
7.24 (16H, m), 7.16−7.13 (2H, m), 5.56 (1H, s), 5.12 (1H, s, J = 2.8
Hz), 4.93 and 4.78 (2H, ABq, J = 11.6 Hz), 4.80 (1H, d, J = 4.0 Hz),
4.82 and 4.47 (2H, ABq, J = 10.8 Hz), 4.57 and 4.51 (2H, ABq, J =
12.0 Hz), 4.31 (1H, dd, J = 4.8, 10.0 Hz), 4.19 (1H, m), 3.99 (1H, dd,
J = 9.2, 9.6 Hz), 3.83 (1H, m), 3.77−3.72 (3H, m), 3.68−3.55 (4H,
m), 3.46 (1H, dd, J = 8.8, 10.0 Hz), 3.42 (3H, s), 3.14 (1H, d, J = 7.6
Hz), 2.41 (1H, d, J = 9.2 Hz); 13C{1H} NMR (100 MHz, CDCl3) δ
138.7, 138.0, 137.7, 136.8, 129.0, 128.3, 128.2, 127.8, 127.6, 127.5,
125.8, 101.4, 100.2, 100.1, 83.4, 80.4, 80.1, 77.3, 75.1, 74.9, 73.4, 71.7,
70.9, 68.9, 68.7, 62.2, 55.4; HRMS (ESI-TOF) m/z [M + Na]+ calcd
for C41H46O11Na 737.2938, found 737.2928.
Compound 17α: white solid; mp 166−167 °C; Rf 0.35 (1:1 n-
hexane/EtOAc); [α]D27 +109.6° (c 0.98, CHCl3); 1H NMR (400
MHz, CDCl3) δ 7.52−7.48 (2H, m), 7.40−7.24 (16H, m), 7.15−7.12
(2H, m), 5.53 (1H, s), 4.98 (1H, d, J = 3.6 Hz), 4.97 and 4.84 (2H,
ABq, J = 11.6 Hz), 4.85 (1H, d, J = 5.6 Hz), 4.81 and 4.49 (2H, ABq,
J = 10.8 Hz), 4.63 and 4.48 (2H, ABq, J = 12.0 Hz), 4.29 (1H, m),
4.12 (1H, m), 4.05 (1H, dd, J = 8.0, 8.8 Hz), 3.85−3.61 (8H, m), 3.48
(1H, dd, J = 8.8, 9.6 Hz), 3.43 (3H, s), 2.89 (1H, d, J = 2.4 Hz), 2.41
(1H, d, J = 9.6 Hz); 13C{1H} NMR (100 MHz, CDCl3) δ 138.7,
138.0, 137.8, 137.0, 129.2, 128.3 × 2, 127.9 × 3, 127.7 × 2, 127.6,
126.3, 102.0, 97.8, 97.7, 83.2, 81.2, 78.3, 77.2, 75.3, 75.1, 73.4, 72.8,
70.9, 69.3, 68.9, 68.3, 62.0, 55.3; HRMS (ESI-TOF) m/z [M + H]+
calcd for C41H47O11 715.3118, found 715.3107.
Compound 22A and 22B. To a solution of 10 (0.56 mg, 6.25
μmol) and 2211 (10.4 mg, 31.2 μmol) in dry MeCN (0.2 M, 313 μL)
was added a solution of 14 (27.0 mg, 62.5 μmol) in dry MeCN (0.2
M, 313 μL) at room temperature under an Ar atmosphere. After the
reaction mixture was stirred for 4 h, the reaction was quenched by the
addition of 50 mM NaBO3 (aq, 6.86 μmol). The aqueous layer was
extracted with EtOAc (3 mL × 5), and then the combined extracts
were washed with sat. NH4Cl (aq, 2 mL), sat. NaHCO3 (aq, 2 mL),
and brine, dried over anhydrous Na2SO4, and concentrated in vacuo.
The residue was purified by preparative TLC (4:1 toluene/EtOAc) to
afford 22A (18.4 mg, 24.0 μmol, 77% yield) and 22B (1.6 mg, 2.18
μmol, 7% yield).
Compound 22A: colorless syrup; Rf 0.57 (2:1 n-hexane/EtOAc);
[α]2D5 +61.6° (c 1.20, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.39−
7.38 (2H, m), 7.34−7.25 (11H, m), 7.14−7.12 (2H, m), 5.04 (1H, d,
J = 3.5 Hz), 5.03 and 4.76 (2H, ABq, J = 11.0 Hz), 4.83 and 4.45 (2H,
ABq, J = 11.0 Hz), 4.75 (1H, d, J = 5.5 Hz), 4.56 and 4.52 (2H, ABq,
J = 12.5 Hz), 4.15−4.12 (2H, m), 3.88 (1H, dd, J = 10.0, 10.0 Hz),
3.81−3.69 (5H, m), 3.66 (1H, dd, J = 2.0, 10.0 Hz), 3.58−3.53 (2H,
m), 3.45−3.41 (4H, m), 3.30 (1H, d, J = 5.5 Hz), 3.03 (1H, d, J =
10.0 Hz), 1.07 (9H, s), 1.01 (9H, s); 13C{1H} NMR (125 MHz,
CDCl3) δ 138.8, 138.0, 137.7, 128.4, 128.3 × 2, 128.0, 127.9, 127.8,
127.7 × 2, 127.5, 101.5, 99.8, 85.1, 83.9, 76.2, 75.3, 75.1, 74.2, 73.4,
71.5, 71.2, 68.7, 66.6, 66.0, 55.6, 27.5, 26.9, 22.7, 19.9; HRMS (ESI-
TOF) m/z [M + Na]+ calcd for C42H58O11SiNa 789.3646, found
789.3622.
Compound 24B: white solid; mp 125−126 °C; Rf 0.36 (4:1
toluene/acetone); [α]D25 +103.8° (c 0.95, CHCl3); H NMR (400
1
MHz, CDCl3) δ 7.39−7.27 (13H, m), 7.15−7.13 (2H, m), 4.96−4.88
(3H, m), 4.84−4.79 (3H, m), 4.59 and 4.48 (2H, ABq, J = 12.4 Hz),
4.48 (1H, ABq, J = 12.8 Hz), 4.25 (1H, dd, J = 4.8, 12.4 Hz), 4.10−
4.06 (2H, m), 3.94 (1H, dd, J = 9.2, 9.2 Hz), 3.90 (1H, m), 3.78−3.66
(5H, m), 3.58 (1H, dd, J = 9.2, 9.2 Hz), 3.41 (3H, s), 3.03 (1H, br-s),
2.35 (1H, br-s), 2.08 (3H, s), 2.07 (3H, s); 13C{1H} NMR (100
MHz, CDCl3) δ 170.7, 170.3, 138.6, 138.0, 137.7, 128.4, 127.9 × 2,
127.7, 127.6, 97.9, 97.3, 83.2, 78.6, 77.2, 75.3, 75.0, 73.5, 72.7, 71.0,
Compound 22B: colorless syrup; Rf 0.49 (2:1 n-hexane/acetone);
[α]2D5 +37.2° (c 0.46, CHCl3); 1H NMR (500 MHz, CDCl3) δ 7.39−
7.38 (2H, m), 7.35−7.24 (11H, m), 7.16−7.14 (2H, m), 4.98 and
E
J. Org. Chem. XXXX, XXX, XXX−XXX