T. Kitawaki et al. / Tetrahedron 62 (2006) 6792–6801
6797
4.2.6. N-Cyclohexylcarbazole (3e)21 (Table 2, entry 7).
The general procedure using cyclohexylamine (1e)
(0.0229 mL, 0.200 mmol), dibromobiphenyl (2) (68.6 mg,
0.220 mmol), Pd2(dba)3 (18.3 mg, 0.0200 mmol), 2-(di-tert-
butylphosphino)binaphthyl (8) (23.9 mg, 0.0600 mmol),
NaOt-Bu (57.7 mg, 0.600 mmol), and toluene (0.8 mL)
gave N-cyclohexylcarbazole (3e) (40.0 mg, 80%) as a color-
less solid: Rf¼0.53 (toluene/hexane¼1:5); mp 143–144 ꢀC
7.26–7.38 (m, 13H), 7.47–7.51 (m, 2H); 13C NMR d 67.3,
69.0, 75.2, 75.5, 82.1, 82.1, 86.8, 101.1, 126.1, 127.8,
127.9, 128.2, 128.3, 128.3, 128.4, 128.5, 129.0, 137.5,
138.3, 138.6; IR n 3400, 3335 cmꢁ1; MS m/z 447 (M+,
1%), 356 (2), 248 (37), 91 (100); HRMS Calcd for
C27H29NO5 (M+): 447.2046. Found: 447.2056. Anal. Calcd
for C27H29NO5: C, 72.46; H, 6.53; N, 3.13%. Found: C,
72.32; H, 6.55; N, 2.74%.
1
(lit.21 mp 143 ꢀC); H NMR d 1.31–1.61 (m, 3H), 1.82–
1.87 (m, 1H), 1.94–2.04 (m, 4H), 2.33–2.47 (m, 2H), 4.49
(tt, J¼12.3, 3.9 Hz, 1H), 7.20 (dd, J¼7.8, 7.6 Hz, 2H), 7.43
(ddd, J¼8.1, 7.6, 1.2 Hz, 2H), 7.56 (d, J¼8.1 Hz, 2H), 8.10
(dd, J¼7.6, 1.2 Hz, 2H); 13C NMR d 25.8, 26.7, 30.9, 55.5,
110.4, 118.6, 120.4, 123.4, 125.4, 139.8; IR (KBr) n 3055,
2920, 1590, 1455 cmꢁ1; MS m/z 249 (M+, 100%), 206 (43),
167 (92); HRMS Calcd for C18H19N (M+): 249.1517.
Found: 249.1517. Anal. Calcd for C18H19N: C, 86.70; H,
7.68; N, 5.62%. Found: C, 86.48; H, 7.60; N, 5.58%.
4.2.8. 2,3-Di-O-benzyl-4,6-O-benzylidene-a- and b-D-
glucopyranosylcarbazole (3f) (Table 2, entry 8). Ar gas
was bubbled into a mixture of glucosylamine (1f) (20 mg,
0.0447 mmol), dibromobiphenyl (2) (42.0 mg, 0.135 mmol),
Pd2(dba)3 (41 mg, 0.0447 mmol), 2-(di-tert-butylphosphino)-
binaphthyl (8) (53.0 mg, 0.133 mmol), and NaOt-Bu
(12.9 mg, 0.134 mmol) in toluene (0.8 mL) for 15 min. The
reaction mixture was then heated at 60 ꢀC in a sealed tube
for 24 h. After cooling, the mixture was purified by column
chromatography (silica gel: 2 g, EtOAc/hexane¼1:40) to
afford an anomeric mixture of glucosylcarbazole (3f). The
mixture was separated by preparative TLC using EtOAc/
hexane¼1:8 as an eluent to give a-anomer (3fa)9 (5.1 mg,
19%) as a colorless syrup and b-anomer (3fb) (8.9 mg,
33%) as a colorless syrup. Data for 3fa: Rf¼0.23 (EtOAc/
4.2.7. 2,3-Di-O-benzyl-4,6-O-benzylidene-b-D-gluco-
pyranosylamine (1f). To a suspension of NaH (39 mg,
1.63 mmol) in DMF (2 mL) was slowly added 4,6-O-benzyl-
idene-b-D-glucopyranosylazide22 (120 mg, 0.409 mmol) at
0 ꢀC. After stirring at rt for 5 min, the reaction mixture
was cooled to 0 ꢀC. To this mixture was slowly added benzyl
bromide (0.15 mL, 1.26 mmol), and the mixture was stirred
at rt for 2 h. After addition of MeOH at 0 ꢀC, the reaction
mixture was diluted with EtOAc and washed with H2O
and brine. The organic layer was dried and concentrated to
give a residue, which was purified by column chromato-
graphy (silica gel: 6 g, EtOAc/hexane¼1:20) to afford
2,3-O-benzyl-4,6-O-benzylidene-b-D-glucopyranosylazide
(176 mg, 90%) as a white solid: Rf¼0.88 (EtOAc/tol-
uene¼1:2); mp 112 ꢀC; [a]D27 +69.5 (c 1.0, CHCl3); 1H
NMR d 3.36 (dd, J¼8.7, 8.4 Hz, 1H), 3.42 (ddd, J¼9.9,
9.6, 4.8 Hz, 1H), 3.64 (dd, J¼9.6, 9.3 Hz, 1H), 3.69 (dd,
J¼10.5, 9.9 Hz, 1H), 3.75 (dd, J¼9.3, 8.7 Hz, 1H), 4.32
(dd, J¼10.5, 4.8 Hz, 1H), 4.65 (d, J¼8.4 Hz, 1H), 4.77
and 4.92 (2d, J¼11.4 Hz, each 1H), 4.81 (s, 2H), 5.52 (s,
1H), 7.25–7.33 (m, 13H), 7.45–7.48 (m, 2H); 13C NMR
d 68.1, 68.4, 75.2, 75.7, 81.2, 81.3, 81.4, 90.6, 101.2,
126.0, 127.8, 128.0, 128.1, 128.3, 128.3, 128.4, 128.5,
129.1, 137.1, 137.7, 138.2; IR n 2115 cmꢁ1; MS m/z 473
(M+, 1%), 431 (1), 382 (18), 91 (100); HRMS Calcd for
C27H27N3O5 (M+): 473.1951. Found: 473.1960. Anal.
Calcd for C27H27N3O5: C, 68.48; H, 5.75; N, 8.87%.
Found: C, 68.51; H, 5.86; N, 8.64%.
1
hexane¼1:8); [a]D21 ꢁ14.5 (c 0.1, CHCl3); H NMR (C6D6)
d 3.50 (dd, J¼10.5, 10.2 Hz, 1H), 3.73 and 3.83 (2d,
J¼11.9 Hz, each 1H), 3.93 (br d, J¼1.8 Hz, 1H), 4.02–4.07
(m, 2H), 4.30 (dd, J¼10.5, 5.1 Hz, 1H), 4.42 and 4.53 (2d,
J¼12.2 Hz, each 1H), 4.60–4.71 (m, 1H), 5.39 (s, 1H), 6.47
(d, J¼1.8 Hz, 1H), 6.54 (d, J¼6.3 Hz, 2H), 6.81–6.90 (m,
4H), 7.11–7.36 (m, 11H), 7.65 (br d, J¼7.8 Hz, 4H), 8.03
(d, J¼7.5 Hz, 2H); IR (neat) n 3030, 2920, 1455 cmꢁ1; MS
m/z 597 (M+, 13%), 167 (23), 91 (100); HRMS Calcd for
C39H35NO5 (M+): 597.2515. Found: 597.2522. Data for
3fb: Rf¼0.20 (EtOAc/hexane¼1:8); [a]2D5 +31.7 (c 0.97,
CHCl3); 1H NMR d 3.35 (d, J¼10.0 Hz, 1H), 3.79 (m, 1H),
3.93 (dd, J¼10.5, 10.2 Hz, 1H), 4.00–4.08 (m, 2H), 4.06
(d, J¼10.0 Hz, 1H), 4.40 (dd, J¼8.8, 8.8 Hz, 1H), 4.46 (dd,
J¼10.5, 4.9 Hz, 1H), 4.83 (d, J¼11.2 Hz, 1H), 5.00 (d,
J¼11.2 Hz, 1H), 5.73 (s, 1H), 5.88 (d, J¼8.8 Hz, 1H), 6.34
(d, J¼7.6 Hz, 2H), 6.93 (dd, J¼7.6, 7.6 Hz, 2H), 7.05 (dd,
J¼7.6, 7.6 Hz, 1H), 7.28–7.64 (m, 16H), 8.09 (d, J¼7.6 Hz,
2H); 13C NMR d 68.9, 69.4, 75.2, 75.6, 78.8, 82.0, 82.4,
85.5, 101.5, 109.8, 112.8, 120.4, 126.2, 127.8, 127.9, 128.1,
128.2, 128.5, 128.6, 129.2, 136.7, 137.4, 138.5; IR (neat)
n 3030, 2875, 1455 cmꢁ1; MS m/z 597 (M+, 6%), 167 (12),
91 (100); HRMS Calcd for C39H35NO5 (M+): 597.2515.
Found: 597.2513.
To a solution of 2,3-O-benzyl-4,6-O-benzylidene-b-D-gluco-
pyranosylazide (136 mg, 0.287 mmol) in toluene (4 mL)
was added Lindlar catalyst (70 mg). The reaction mixture
was stirred for 12 h under H2 atmosphere (1 atm) at rt.
Then the catalyst was removed by filtration through Celite
and the filtrate was concentrated to give a residue, which
was recrystallized from EtOH to afford glucosylamine 1g
(98.5 mg, 76%) as a white solid: Rf¼0.34 (EtOAc/
toluene¼1:2); mp 111–112 ꢀC (decomp.); [a]D27 ꢁ38.7 (c
4.2.9. N-tert-Butylcarbazole (3g) (Table 2, entry 10). The
general procedure using 2-(dicyclohexylphosphino)-20,40,60-
triisopropylbiphenyl (6) gave N-(tert-butyl)carbazole (3g)
(23.6 mg, 42%) as a colorless solid: Rf¼0.38 (toluene/
1
hexane¼1:5); mp 122–123 ꢀC; H NMR d 2.00 (s, 9H),
7.19 (ddd, J¼7.8, 7.1, 0.7 Hz, 2H), 7.37 (ddd, J¼8.7, 7.1,
1.5 Hz, 2H), 7.86 (dd, J¼8.7, 0.7 Hz, 2H), 8.10 (dd,
J¼7.8, 1.5 Hz, 2H); 13C NMR d 31.2, 59.2, 113.9, 118.6,
120.0, 124.6, 125.2, 140.6; IR (KBr) n 3050, 2970, 1590,
1440 cmꢁ1; MS m/z 223 (M+, 17%), 167 (100), 140 (16);
HRMS Calcd for C16H17N (M+): 223.1361. Found:
223.1359. Anal. Calcd for C16H17N$0.1H2O: C, 85.37; H,
7.70; N, 6.22%. Found: C, 85.34; H, 7.63; N, 6.29%.
1
1.0, CHCl3); H NMR d 1.91 (br s, 2H), 3.21 (dd, J¼8.6,
8.6 Hz, 1H), 3.42 (ddd, J¼9.6, 9.3, 5.0 Hz, 1H), 3.65 (dd,
J¼9.3, 9.1 Hz, 1H), 3.71 (dd, J¼10.4, 9.6 Hz, 1H), 3.80
(dd, J¼9.1, 8.6 Hz, 1H), 4.22 (d, J¼8.6 Hz, 1H), 4.32 (dd,
J¼10.4, 5.0 Hz, 1H), 4.80 and 4.94 (2d, J¼11.4 Hz, each
1H), 4.84 and 4.92 (2d, J¼10.5 Hz, each 1H), 5.56 (s, 1H),