2
992
P. Kasák, M. Widhalm
PAPER
CH ), 28.03 (CH ), 27.9 (CH ), 26.50 (d, J = 9.1 Hz, CH ), 26.03 (d,
J = 4.6, 7.3 Hz, 6 H), 1.14 (dd, J = 3.3, 7.2 Hz, 6 H), 0.91–0.00 (m,
2
2
2
2
J = 7.7 Hz, CH2).
6 H).
3
1
13
P NMR (162 MHz, CDCl ): d = 31.71 (m).
C NMR (100 MHz, CDCl ): d = 138.02 (C), 137.89 (C), 128.39,
3
3
MS (EI, 70 eV, 200 °C): m/z (%) = 469 (6) [M+].
128.35, 127.76, 127.70, 127.64, 73.18 (CH ), 73.14 (CH ), 71.31 (d,
J = 3.6 Hz, CH ), 71.21 (CH ), 28.63 (d, J = 31.6 Hz), 28.12 (d,
J = 31.6 Hz), 22.79 (dd, J = 12.3, 30.5 Hz, CH ), 18.28 (CH ),
2 2
2
2
HRMS (EI): m/z calcd for C H BP : 455.3282; found: 455.3296.
2
8
47
2
2 2
1
2.49 (CH ), 12.20 (d, J = 2.3 Hz, CH ).
3 3
1
,3-Bis[(2R,5R)-2,5-dimethylphospholan-1-yl]propane–Bis(bo-
3
1
P NMR (162 MHz, CDCl ): d = 29.57 (m).
3
rane) Complex (12)
Yield: 86%; mp 86–90 °C; [a]D +12.2 (c 1.0, CHCl3).
2
0
MS (EI, 70 eV, 250 °C): m/z (%) = 729 (7) [M+].
1
H NMR (400 MHz, CDCl ): d = 2.19–1.97 (m, 8 H), 1.85–1.71 (m,
HRMS (EI): m/z calcd for C H O BP : 714.4138; found:
714.4152.
3
43 61
4
2
2
6
H), 1.69–1.54 (m, 4 H), 1.32 (m, 4 H), 1.22 (dd, J = 7.4, 15.9 Hz,
H), 1.15 (dd, J = 7.1, 13.6 Hz, 6 H), 0.91–0.00 (m, 6 H).
1
3
1,3-Bis({(R,R)-bis[2-(benzyloxy)-1-methylethyl]phospha-
nyl}methyl)benzene–Bis(borane) Complex (16) by Deprotona-
tion Followed by Alkylation (Method B); Typical Procedure
Borane complex 5 (310 mg, 0.90 mmol) was dissolved in anhyd
THF (4 mL) and the soln was cooled to 0 °C. To this 1.6 M n-BuLi
in hexane (0.6 mL, 0.95 mmol) was added dropwise and the mixture
was stirred for 20 min at 0 °C. The temperature was lowered to
C NMR (100 MHz, CDCl ): d = 34.83 (d, J = 3.1 Hz, CH ), 34.39
2
3
2
(
CH ), 33.64 (d, J = 37.0 Hz), 32.08 (d, J = 33.7 Hz), 23.20 (dd,
J = 11.5, 26.7 Hz, CH ), 16.66 (CH ), 15.72 (d, J = 4.6 Hz, CH ),
1
2
2
3
3.36 (d, J = 2.3 Hz, CH3).
1
3
P NMR (162 MHz, CDCl ): d = 38.68 (m).
3
MS (EI, 70 eV, 80 °C): m/z (%) = 299 (34) [M+].
–
78 °C and 1,3-bis(bromomethyl)benzene (119 mg, 0.45 mmol) in
HRMS (EI): m/z calcd for C H BP : 285.2075; found: 285.2066.
1
5
32
2
THF (2.5 mL) was added and the mixture was allowed to warm to
r.t. After quenching with 1 M HCl (5 mL) and extractive workup
with CH Cl (2 × 25 mL), the crude diborane complex was purified
1
,3-Bis{[(2R,5R)-2,5-dimethylphospholan-1-yl]methyl}ben-
2
2
zene–Bis(borane) Complex (13)
by column chromatography (silica gel, Et O–PE, 10:90 to 30:70);
2
0
2
Yield: 90%; mp 116–120 °C; [a]D +127 (c 1.0, CHCl3)
1
this yielded 16.
H NMR (400 MHz, CDCl ): d = 7.27–7.13 (m, 4 H), 2.97 (dd,
3
Yield: 226 mg (64%); colorless oil.
Compound 16 can also be prepared by Method A.
J = 8.5, 13.4 Hz, 2 H), 2.75 (dd, J = 13.7, 14.7 Hz, 2 H), 2.22–2.03
(
(
1
m, 8 H), 1.47–1.26 (m, 4 H), 1.26 (dd, J = 7.2, 13.4 Hz, 6 H), 0.81
dd, J = 7.2, 16.5 Hz, 6 H), 0.91–0.00 (m, 6 H).
Chromatography (silica gel, Et O–PE, 30:70); yield: 90%; colorless
2
2
0
3
oil; [a]D +20.1 (c 1.0, CHCl3).
C NMR (100 MHz, CDCl ): d = 132.65 (dd, J = 2.3, 4.7 Hz, C),
3
1
4
(
31.96 (t, J = 4.0 Hz), 128.60 (t, J = 2.1 Hz), 128.44 (dd, J = 3.2,
.2 Hz), 34.60 (d, J = 2.7 Hz, CH ), 34.41 (d, J = 35.2 Hz), 34.35
CH ), 30.72 (d, J = 32.9 Hz), 28.73 (d, J = 23.3 Hz, CH ), 15.48 (d,
1
H NMR (400 MHz, CDCl ): d = 7.34–7.22 (m, 20 H), 7.15–7.07
3
2
(m, 4 H), 4.40 (d, J = 12.5 Hz, 2 H), 4.40 (br s, 4 H), 4.37 (d,
J = 12.5 Hz, 2 H), 3.65 (ddd, J = 5.1, 9.5, 11.8 Hz, 2 H), 3.61–3.44
(m, 8 H), 3.15 (dd, J = 13.1, 13.5 Hz, 2 H), 3.08 (dd, J = 13.1, 14.0
Hz, 2 H), 2.35–2.16 (m, 4 H), 1.19 (pseudo t, J = 7.3 Hz, 6 H), 1.16
2
2
J = 4.0 Hz, CH ), 13.28 (d, J = 2.7 Hz, CH ).
3
3
3
1
P NMR (162 MHz, CDCl ): d = 39.50 (m).
3
(pseudo t, J = 7.4 Hz, 6 H), 0.91–0.00 (m, 6 H).
MS (EI, 70 eV, 100 °C): m/z (%) = 362 (15) [M+].
1
3
C NMR (100 MHz, CDCl ): d = 138.00 (C), 137.98 (C), 133.53
3
HRMS (EI): m/z calcd for C H B P : 362.2642; found: 362.2648.
2
0
38
2 2
(
dd, J = 2.3, 5.4 Hz), 131.87 (pseudo t, J = 4.2 Hz), 128.84 (m),
1
2
28.36, 128.30 (m), 127.75, 127.66, 73.13 (CH ), 71.23 (m, CH ),
2
2
1
,2-Bis{[(2R,5R)-2,5-dimethylphospholanyl]methyl}benzene–
9.32 (d, J = 28.2 Hz, CH ), 28.42 (d, J = 30.0 Hz), 28.02 (d,
2
Bis(borane) Complex (14)
Yield: 80%; mp 163–167 °C; [a]D +211 (c 0.33, CHCl3).
J = 29.5 Hz), 12.56 (d, J = 1.5 Hz, CH ), 12.42 (d, J = 2.0 Hz, CH ).
2
0
3
3
3
1
P NMR (162 MHz, CDCl ): d = 31.27 (m).
1
3
H NMR (400 MHz, CDCl ): d = 7.18–7.09 (m, 4 H), 3.62 (dd,
3
MS (EI, 50 eV, 260 °C): m/z (%) = 790 (1) [M+].
J = 6.9, 14.7 Hz, 2 H), 2.77 (pseudo t, J = 15.2 Hz, 2 H), 2.26–2.06
(
(
1
m, 8 H), 1.49–1.34 (m, 4 H), 1.32 (dd, J = 6.4, 13.0 Hz, 6 H), 0.86
dd, J = 6.9, 15.7 Hz, 6 H), 0.8 to –0.1 (m, 6 H).
ESI-HRMS: m/z calcd for C H B NaO P : 813.4520; found:
4
8
66
2
4 2
8
13.4549.
3
C NMR (100 MHz, CDCl ): d = 132.82 (t, J = 4.4 Hz, C), 130.58
3
(
2R,5R)-2,5-Bis{(R,R)-bis[2-(benzyloxy)-1-methylethyl]phos-
(
dd, J = 2.4, 3.8 Hz), 127.06 (t, J = 2.5 Hz), 34.70 (d, J = 3.4 Hz,
phanyl}hexane–Bis(borane) Complex (17)
CH ), 34.44 (CH ), 34.34 (d, J = 35.5 Hz), 32.05 (d, J = 33.2 Hz),
2
2
Borane complex 5 (230 mg, 0.67 mmol) was dissolved in anhyd
THF (4 mL) and the soln was cooled to 0 °C. A soln of 2.5 M n-
BuLi in hexane (0.3 mL, 0.75 mmol) was added dropwise over 15
min and the soln was stirred for 30 min at 0 °C. This was followed
by slow addition of (2S,5S)-hexane-2,5-diyl dimesylate (88 mg,
2
7.17 (d, J = 22.3 Hz, CH ), 15.11 (d, J = 3.9 Hz, CH ), 13.69 (d,
2
3
J = 2.5 Hz, CH3).
3
1
P NMR (162 MHz, CDCl ): d = 38.68 (m).
3
MS (EI, 70 eV, 110 °C): m/z (%) = 362 (33) [M+].
0
.32 mmol) in THF (2 mL) and once addition was complete, the re-
HRMS (EI): m/z calcd for C H B P : 362.2642; found: 362.2635.
2
0
38
2 2
action mixture was heated to 55 °C for 3 h. The cooled reaction
mixture was added dropwise to ice-cold 1 M aq HCl (5 mL) and the
aqueous phase was extracted with Et O (2 × 25 mL) and the organic
layers were combined, dried (MgSO ), and filtered. The solvent was
evaporated to give a colorless oil, which was purified by flash chro-
matography (silica gel, Et O–PE, 50:50).
1
,3-Bis{(R,R)-bis[2-(benzyloxy)-1-methylethyl]phospha-
2
nyl}propane–Bis(borane) Complex (15)
4
Chromatography (silica gel, Et O–PE, 30:70); yield: 91%; colorless
2
20
oil; [a]D +10.1 (c 1.0, CHCl3).
2
1
H NMR (400 MHz, CDCl ): d = 7.33–7.22 (m, 20 H), 4.45 (d,
3
2
0
Yield: 111 mg (45%); colorless oil; [a]D +17.3 (c 2.0, CHCl3).
J = 11.9 Hz, 2 H), 4.43 (br s, 4H), 4.41 (d, J = 11.9 Hz, 2 H), 3.72–
1
3
.50 (m, 8 H), 2.28–2.17 (m, 4 H), 1.80–1.62 (m, 6 H), 1.17 (dd,
H NMR (400 MHz, CDCl ): d = 7.35–7.23 (m, 20 H), 4.42 (m, 4
3
H), 4.39 (br s, 4 H), 3.69 (m, 4 H), 3.52 (m, 4 H), 2.39 (m, 2 H), 2.24
Synthesis 2007, No. 19, 2987–2994 © Thieme Stuttgart · New York