M. Gerdin et al. / Journal of Organometallic Chemistry 693 (2008) 3519–3526
3525
(d, JC–P = 6.5 Hz), 25.4 (d, JC–P = 8.8 Hz); 31P NMR (202 MHz, CDCl3)
4.8.3. Compound 23c
d 61.0, 59.2.
Compound 23c was purified on silica gel using a gradient of 2–
5% Et2O in hexane. Yield 20%, major isomer. 1H NMR (CDCl3) d 0.41
(s, 3H), 0.43 (s, 3H), 1.35–1.42 (m, 1H), 1.70–1.76 (m, 1H), 1.84 (d,
J = 9.7 Hz, 1H), 1.92–2.18 (m, 3H), 2.71–2.80 (m, 1H), 4.87 (d,
J = 9.6 Hz, 1H), 5.44–5.51 (m, 1H), 6.00 (dt, J = 3.2, 0.9 Hz, 1H),
6.03–6.10 (m, 1H), 6.27 (dd, J = 3.20, 1.82 Hz, 1H), 7.27–7.30 (m,
1H), 7.32–7.40 (m, 3H), 7.52–7.61 (m, 2H). Spectrum contains
around 24% of the minor isomer.
4.7. Compound 16
Inside
0.027 mmol) was weighed into a flask. DMAP (0.77 mg, 6.2
and (S)-MTPA-Cl (10 l, 62 L) were then added. Pyridine
(120 L) was added via a syringe and the solution was stirred at
a
nitrogen filled glovebox compound 15 (6.74 mg,
l
L)
l
l
l
r.t. for 16 h. The resulting product was taken up in EtOAc (20 mL)
and washed with sat. NaHCO3 (2 ꢂ 10 mL) and NH4Cl (2 ꢂ 10 mL)
solutions and brine (2 ꢂ 10 mL). The organic phase was dried over
MgSO4, filtered, and the solvents were evaporated in vacuo to yield
the title compound. The enantiomeric excess was determined by
HPLC [CHIRALCEL OD-H, 0.025% i-PrOH/hexane, 1 mL/min]. 1H
NMR (CDCl3) d 7.52–7.48 (m, 4H), 7.39–7.36 (m, 6H), 5.75–5.67
(m, 2.5H), 5.61–5.55 (m, 0.5H), 0.27 (s, 6H).
4.8.4. Compound 23d
Compound 23d was purified on silica gel using gradient of 5–
40% DCM in hexane. Yield 82%, major (maj) + minor (min) isomer
(65:35 d.r.). 1H NMR (CDCl3) d 0.38 (s, 3H, maj), 0.42 (s, 3H, min),
0.44 (s, 3H, min), 0.51 (s, 3H, maj), 1.18–1.59 (m, overlapping),
1.71–2.28 (m, overlapping), 2.40–2.48 (m, 1H, maj), 2.53–2.65
(m, 1H, min), 4.36 (dd, J = 10.0, 4.1 Hz, 1H, min), 4.84 (d,
J = 8.8 Hz, 1H, maj), 4.99 (ddt, J = 10.0, 4.3, 2.1 Hz, 1H, min), 5.18–
5.28 (m, 1H, maj), 5.56–5.64 (m, 1H, min), 6.02–6.12 (m, 1H,
maj), 6.63–6.78 (m, 2H, maj), 6.81–6.91 (m, 2H, maj), 6.92–7.03
(m, 2H, min), 7.13–7.22 (m, 2H, min), 7.30–7.68 (m, overlaping),
7.78–7.82 (m, 1H, min). 13C NMR (CDCl3) d ꢁ4.80 (maj), ꢁ2.90
(min), ꢁ2.76 (maj), ꢁ1.86 (min), 20.5 (maj), 21.3 (min), 24.8
(maj), 25.7 (min), 26.1 (maj), 26.3 (min), 26.4 (maj), 42.5 (maj),
44.7 (min), 74.5 (maj), 75.5 (min), 114.5 (maj), 114.6 (maj), 114.9
(min), 115.1 (min), 123.9 (maj), 126.3 (maj), 126.4 (maj), 127.77
(min), 127.84 (maj), 128.1 (maj), 128.42 (min), 128.49 (min),
128.53 (min), 128.66 (min), 129.1 (maj), 129.2 (min), 133.5
4.8. General procedure for allylboration of aldehydes
Inside
0.15 mmol) was weighed into a vial [28]. 1,2-Dichlorobenzene
(500 L) and aldehyde (1.5 mmol) were then added and the vial
a nitrogen filled glovebox compound 3 (51.3 mg,
l
was capped. Heating was performed outside the glovebox in a
microwave reactor. 1-Methoxynapthalene (23.7 mg, 0.15 mmol)
and 2 mL of water were then added and the mixture stirred for
15 min. Et2O (10 mL) was added and the phases separated. The
water phase was then repeatedly extracted with Et2O
(3 ꢂ 10 mL) and the combined organic phases dried over MgSO4,
filtered, the solvents were evaporated and a 1H NMR spectrum
was recorded. The crude product was then dried under vacuum
to remove remaining 1,2-dichlorobenzene. Purification was per-
formed using gradient chromatography yielding the products as
colorless oils.
2
2
(maj), 133.9 (d, JC–F = 25.4 Hz, maj), 134.1 (d, JC–F = 23.6, min),
3
3
138.4 (maj), 139.5 (d, JC–F = 3.1 Hz, min), 140.4 (d, JC–F = 3.1 Hz,
maj), 141.0 (min), 161.5 (d, JC–F = 244.3 Hz, maj), 162.8 (d, JC–F
245.4 Hz, min).
1
1
=
4.8.5. Compound 23e
Compound 23e was purified on silica gel using a gradient of
11–50% DCM in hexane. Yield 66%, major + minor isomer. Major
isomer: 1H NMR (CDCl3) d 0.33 (s, 3H), 0.37 (s, 3H), 0.52 (app.
qd, J = 12.2, 3.8 Hz, 1H), 0.76 (app. qd, J = 12.5, 3.3 Hz, 1H), 1.04
(d, J = 9.5 Hz, 1H), 1.06–1.34 (m, 6H), 1.39–1.49 (m, 1H), 1.52–
1.61 (m, 2H), 1.63–1.77 (m, 2H), 1.89–2.18 (m, 4H), 2.45–2.50
(m, 1H), 3.27 (app t, J = 9.0 Hz, 1H), 5.63–5.70 (m, 1H), 5.99–
6.07 (m, 1H), 7.32–7.39 (m, 3H), 7.50–7.57 (m, 2H); 13C NMR
(CDCl3) d ꢁ3.9, ꢁ3.3, 20.6, 25.9, 26.1, 26.2, 26.3, 26.7, 29.3, 29.6,
36.1, 42.6, 78.7, 125.5, 127.7, 128.8, 132.6, 133.85, 138.94.
Anal. Calc. for C21H32OSi: C, 76.77; H, 9.82. Found: C, 76.65; H,
9.77%.
4.8.1. Compound 23a
Compound 23a was purified on alumina (activity grade II) using
gradient of 1–5% EtOAc in hexane. Yield 75%, major + minor isomer
(5 h r ꢂ n time). Major and minor isomer were then separated on
silica using a gradient of 2–5% EtOAc in hexane. Major isomer:
1H NMR (CDCl3) d 0.39 (s, 3H), 0.51 (s, 3H), 1.35–1.50 (m, 1H),
1.70–1.90 (m, 1H), 1.83 (d, J = 8.9 Hz, 1H), 1.95–2.30 (m, 3H)
2.43–2.55 (m, 1H), 4.89 (d, J = 8.9 Hz,1H), 5.18–5.30 (m, 1H),
5.97–6.10 (m, 1H), 6.70–6.88 (m, 2H), 7.10–7.22 (m, 3H), 7.58–
7.70 (m, 3H), 7.87–7.98 (m, 2H); 13C NMR (CDCl3) d ꢁ4.6, ꢁ2.9,
20.5, 26.2, 26.6, 42.4, 75.0, 124.2, 124.8, 126.4, 127.8, 128.1,
129.0, 133.1, 134.0, 138.5, 144.7. Anal. Calc. for C21H26Osi: C,
78.21; H, 8.13. Found: C, 78.11; H, 8.09%.
Minor isomer: 1H NMR (CDCl3) d 0.30 (s, 3H), 0.34 (s, 3H), 0.78
(d, J = 7.2 Hz, 1H), 0.83–1.90 (m, 14H), 1.93–2.11 (m, 2H), 2.30–
2.37 (m, 1H), 3.20–3.27 (m, 1H), 5.63–5.67 (m, 1H), 5.68–5.75
(m, 1H), 7.32–7.38 (m, 3H), 7.52–7.58 (m, 2H); 13C NMR (CDCl3)
d ꢁ2.4, ꢁ2.3, 21.0, 24.4, 25.4, 26.4, 26.70, 26.76, 26.82, 31.2, 39.0,
40.1, 127.9, 128.6, 128.8, 129.6, 133.8, 141.4. Signal from
RCH(OH)Cy obscured by residual solvent peak.
Minor isomer: 1H NMR (CDCl3) d 0.41 (s, 3H), 0.44 (s, 3H), 1.49
(d, J = 4.9 Hz, 1H), 1.50–1.56 (m, 1H), 1.78–1.90 (m, 2H), 1.92–2.12
(m, 2H), 2.61–2.67 (m, 1H), 4.37 (dd, J = 10.0, 4.9 Hz, 1H), 4.97–5.02
(m, 1H), 5.54–5.61 (m, 1H), 7.19–7.39 (m, 8H), 7.59–7.68 (m, 2H).
13C NMR (CDCl3) d ꢁ2.9, ꢁ1.9, 21.4, 25.7, 26.3, 44.6, 76.2, 126.9,
127.6, 127.8, 128.28, 128.33, 128.6, 129.4, 133.8, 141.2, 143.7.
4.8.6. Compound 23f
4.8.2. Compound 23b
Compound 23f was purified on silica gel using a gradient of 0–
10% Et2O in hexane. Yield 29%, major isomer. 1H NMR (CDCl3) d
0.38 (s, 3H), 0.53, (s, 3H), 1.40–1.51 (m, 1H), 1.77–1.88 (m, 1H),
1.91 (d, J = 9.0 Hz, 1H), 1.96–2.12 (m, 2H), 2.13–2.27 (m, 1H),
2.43–2.50 (m, 1H), 4.88 (d, J = 9.0 Hz, 1H), 5.12–5.19 (m, 1H),
6.04–6.12 (m, 1H), 6.76–6.82 (m, 2H), 7.39–7.48 (m, 5H), 7.61–
7.66 (m, 2H); 13C NMR (CDCl3) d ꢁ5.0, ꢁ2.7, 20.4, 26.1, 26.4, 42.4,
Compound 23b was purified on alumina (activity grade II) using
a gradient of 1–10% Et2O in hexane. Yield 67%, major isomer (91:9
d.r.). Major isomer: 1H NMR (CDCl3) d 0.33 (s, 3H), 0.37 (s, 3H),
0.79–0.85 (t, J = 7.1 Hz, 3H), 1.02–1.42 (m, 8H), 1.65–1.75 (m,
1H), 1.92–2.16 (m, 3H), 2.20–2.26 (m, 1H), 3.60–3.68 (m, 1H),
5.67–5.78 (m, 1H), 5.99–6.08 (m, 1H), 7.29–7.40 (m, 3H), 7.49–
7.59 (m, 2H). 13C NMRCDCl3) d ꢁ3.99, ꢁ3.29, 14.0, 20.6, 22.5,
26.3, 26.8, 28.2, 36.9, 39.6, 74.2, 125.3, 127.8, 128.8, 132.7, 133.8,
138.9. Anal. Calc. for C19H30OSi: C, 75.43; H, 10.00. Found: C,
75.32; H, 9.88%.
1
3
74.5, 123.4, 124.2 (q, JC–F = 271.7 Hz), 124.7 (q, JC–F = 3.7 Hz),
3
125.2, 128.2, 128.7 (q, JC–F = 32.3 Hz), 129.2, 133.96, 134.00,
138.3, 148.8.