H. Tsukamoto et al. / Tetrahedron Letters 48 (2007) 8438–8441
8441
1
3
Dagneau, P.; Grabowski, E. J. J.; Oballa, R.; O’Shea, P.;
Prasit, P.; Robichaud, J.; Tillyer, R.; Wang, X. J. Org.
Chem. 2003, 68, 2633.
J = 5.8 Hz), 2.14 (br s, 1H), 1.78–1.63 (m, 4H); C NMR
(75.4 MHz, CDCl
3
): d 138.2, 128.5, 127.8, 127.7, 73.0,
70.3, 62.6, 30.0, 26.5; IR (neat): mmax (cm ) 3392, 2939,
À1
6
7
8
. Tsukamoto, H.; Sato, M.; Kondo, Y. Chem. Commun.
2863, 1094, 1057, 733, 697; EI-MS m/z (relative intensity)
+
2
004, 1200.
180 (M) (17), 107 (97), 91 (100); EI-HRMS calcd for
+
. Unpublished result. The detailed will be published as full
paper.
C
11
H
16
O
2
(M) 180.1150, found 180.1140. 4-tert-Butyl-
1
dimethylsilyloxybutane-1-ol (5b): H NMR (300 MHz,
. (a) Hall, D. G.; Tailor, J.; Gravel, M. Angew. Chem., Int.
Ed. 1999, 38, 3064; (b) Gravel, M.; Thompson, K. A.; Zak,
M.; B e´ rub e´ , C.; Hall, D. G. J. Org. Chem. 2002, 67, 3; (c)
Mothana, S.; Chahal, N.; Vanneste, S.; Hall, D. G. J.
Comb. Chem. 2007, 9, 193.
CDCl ): d 3.68–3.61 (m, 4H), 2.49 (br s, 1H), 1.69–1.62 (m,
3
1
3
4H), 0.91 (s, 9H), 0.07 (s, 6H); C NMR (75.4 MHz,
CDCl ): d 63.3, 62.7, 30.1, 29.7, 25.8, 18.2, À5.6; IR (neat):
3
À1
m
max (cm ) 3336, 2929, 2858, 1254, 1098, 1061, 834, 774;
+
FAB-MS m/z 205 (M+H) . 4-Methoxymethoxybutan-1-ol
1
9
. PS-DEAM and MP-TMT were purchased from Argonaut
technologies.
(5c): H NMR (300 MHz, CDCl
3
): d 4.64 (s, 2H), 3.70 (t,
2H, J = 5.9 Hz), 3.58 (t, 2H, J = 5.9 Hz), 3.37 (s, 3H),
1
3
1
0. General procedure for Table 1: To a test tube containing 4a
99.5 mg, 0.452 mmol), 2a (66.4 mg, 0.545 mmol), and
Pd(PPh (2.5 mg, 2.2 lmol) was added anhydrous THF
1.0 mL) under argon. The resulting mixture was sealed
3
1.73–1.66 (m, 5H); C NMR (75.4 MHz, CDCl ): d 96.4,
À1
(
67.6, 62.4, 55.1, 29.6, 26.2; IR (neat): mmax (cm ) 3404,
3
)
4
2935, 2873, 1148, 1109, 1038. 4-Acetyloxybutan-1-ol (5d):
1
(
H NMR (300 MHz, CDCl ): d 4.11 (t, 2H, J = 6.3 Hz),
3
with a screw cap and agitated at 80 °C for 12 h. The
3.69 (t, 2H, J = 6.2 Hz), 2.06 (s, 3H), 1.79–1.59 (m, 4H),
1
3
mixture was cooled down to room temperature, and then
1.38 (br s, 1H); C NMR (75.4 MHz, CDCl
3
): d 171.4,
TM
À1
PS-DEAM (1.7 mmol/g, 0.53 g, 0.90 mmol) and THF
64.2, 62.2, 28.9, 24.9, 20.8; IR (neat): mmax (cm ) 3408,
(
5.3 mL) were added to the mixture. The mixture was
2944, 2875, 1735, 1237, 1044. 4-Benzoyloxybutan-1-ol
1
agitated at room temperature for 24 h. The mixture was
filtered and thoroughly washed with THF. The filtrate was
concentrated in vacuo and residue 5a was dissolved in 1,4-
dioxane, ultra pure water, and aqua regia (10 mL) and
subjected to ICP-ES. The reduction in Pd was calculated
on the basis of the residual Pd concentration determined
by ICP-ES.
(5e): H NMR (300 MHz, CDCl
3
): d 8.05 (dd, 2H, J = 1.4,
8.5 Hz), 7.57 (dd, 1H, J = 1.4, 7.4 Hz), 7.45 (dd, 2H,
J = 7.4, 8.5 Hz), 4.38 (t, 2H, J = 6.5 Hz), 3.74 (t, 2H,
1
3
J = 6.3 Hz), 1.93–1.69 (m, 4H), 1.37 (br s, 1H); C NMR
(75.4 MHz, CDCl
3
): d 166.8, 133.0, 130.4, 129.6, 128.4,
À1
64.7, 62.3, 29.1, 25.1; IR (neat): mmax (cm ) 3421, 2946,
2873, 1715, 1270, 1113, 1069, 1027; EI-MS m/z (relative
+
1
1
1. Si–TAAcOH and Si–thiourea were purchased from
SILICYCLE.
2. It is reported that palladium-catalyzed homocoupling of
arylboronic acids occurs in the presence of oxygen. (a)
Moreno-Man a˜ s, M.; Per e´ z, M.; Pleixats, R. J. Org. Chem.
intensity) 194 (M) (3.7), 166 (11), 123 (83), 105 (100), 77
+
(38); EI-HRMS calcd for C11
194.0945.
H
14
O
3
(M) 194.0943, found
16. For complete conversion of 4 to 5, this catalytic system
requires higher catalyst loading and longer reaction
time than the former. The work-up consisting of agitation
with PS-DEAM, filtration, and evaporation must be
repeated twice for complete conversion of partially formed
borates 6 to free alcohols 5. PS-DEAM might capture 5
partially as its borate and decrease isolated yield of 5
slightly.
1
996, 61, 2346; (b) Aramend ´ı a, M. A.; Lafont, F.;
Moreno-Man a˜ s, M.; Pleixats, R.; Roglans, A. J. Org.
Chem. 1999, 64, 3592; (c) Adamo, C.; Amatore, C.;
Ciofini, I.; Jutand, A.; Lakmini, H. J. Am. Chem. Soc.
2
006, 128, 6829, and references therein.
3. Although commercially available polymer-bound triphen-
ylphosphine-Pd(0) (PS-PPh -Pd) was used as a catalyst for
1
3
17. General procedure for Table 2: To a test tube containing 4a
(49.7 mg, 0.226 mmol), 2b (36.4 mg, 0.151 mmol), and 4-
diphenylphophinobenzoic acid (2.1 mg, 6.9 lmol) was
added a solution of Pd(OAc)2 in anhydrous THF
(6.0 mM, 0.38 mL, 2.3 lmol) under argon. The resulting
mixture was sealed with a screw cap and agitated at 80 °C
this purpose, it turned out to be ineffective. Parlow et al.
reported that anthracene-tagged phosphine-palladium(II)
catalyst for Suzuki–Miyaura cross-coupling allowed for
the easy removal of the Pd catalyst along with the
dissociated phosphine ligand and phosphine oxide
byproducts by sequestration through a chemoselective
Diels–Alder reaction with a maleimide resin. Lan, P.;
Berta, D.; Porco, J. A., Jr.; South, M. S.; Parlow, J. J. J.
Org. Chem. 2003, 68, 9678.
for 12 h. The mixture was cooled down to room temper-
TM
ature, and then PS-DEAM
(1.8 mmol/g, 0.25 g,
0.45 mmol) and THF (2.5 mL) were added to the mixture.
The mixture was agitated at room temperature for 12 h.
The mixture was filtered and thoroughly washed with
THF. The filtrate was concentrated in vacuo and the
residue was subjected to the above PS-DEAM treatment
again to give 5a (39.0 mg, 0.216 mmol, 96%). The reduc-
tion in Pd was calculated on the basis of the residual Pd
concentration determined by ICP-ES.
1
1
4. Vinylboronic anhydride pyridine complex and 4-(di-
phenylphosphino)benzoic acid were purchased from
Aldrich.
5. Characterization data for compounds 5a–e. 4-Benzyloxy-
1
butan-1-ol (5a): H NMR (300 MHz, CDCl ): d 7.39–7.27
3
(
m, 5H), 4.53 (s, 2H), 3.66 (t, 2H, J = 5.9 Hz), 3.53 (t, 2H,