Chemistry of Heterocyclic Compounds 2018, 54(3), 329–333
1
twice through a Celite pad. The filtrate was concentrated on
a rotary evaporator to afford the desired imine.
7.5:1.5:1.0). Dark-yellow oil. H NMR spectrum, δ, ppm
(J, Hz): 12.81 (1H, s, OH); 7.75 (1H, d, J = 4.5, H Ar);
7.72 (1H, d, J = 4.9, H Ar); 7.65 (1H, d, J = 8.9, H Ar);
7.42 (1H, ddd, J = 8.5, J = 6.8, J = 1.4, H Ar); 7.28 (1H,
ddd, J = 7.9, J = 6.9, J = 1.0, H Ar); 7.07 (1H, d, J = 8.8,
H Ar); 5.13 (1H, t, J = 8.2, 2'-CH); 3.61–3.42 (3H, m,
(S)-2-{[(tert-Butyldimethylsilyl)oxy]methyl}-3,4-dihydro-
2
H-pyrrole (4). Analytical data are in accordance with the
10
literature.
R 0.48 (petroleum ether – AcOEt, 3:7). Pale-
f
1
yellow oil. H NMR spectrum, δ, ppm (J, Hz): 7.60 (1H, s,
5
-CH); 4.26–4.05 (1H, m, 2-CH); 3.84 (1H, dd, J = 10.1,
O); 2.67–
.30 (2H, m), 1.93–1.80 (1H, m), and 1.76–1.55 (1H, m,
,4-CH ); 0.87 (9H, s, C(CH ); 0.07 (3H, s, SiCH ); 0.05
).
S)-2-(Azidomethyl)-3,4-dihydro-2H-pyrrole (5). R
CH
2
N , 5'-CH); 2.80 (1H, s, NH); 2.52–2.35 (1H, m), 2.20–
3
J = 4.1) and 3.66 (1H, dd, J = 10.1, J = 5.3, CH
2
2.05 (1H, m), 2.00–1.87 (1H, m), and 1.85–1.71 (1H, m,
13
2
3
3',4'-CH ). C NMR spectrum, δ, ppm: 156.0; 132.0;
2
2
3
)
3
3
129.1; 128.9; 128.4; 126.4; 122.4; 120.9; 120.1; 114.8;
(
3H, s, SiCH
3
58.8; 57.2; 56.4; 31.6; 28.2. Found, m/z: 269.1390.
(
f
0.27
petroleum ether – AcOEt, 1:1). Yellow oil. H NMR spectrum,
δ, ppm (J, Hz): 7.63 (1H, s, 5-CH); 4.27–4.12 (1H, m,
-CH); 3.50 (1H, dd, J = 12.3, J = 5.2) and 3.41 (1H, dd,
J = 12.3, J = 5.4, CH ); 2.75–2.57 (1H, m), 2.57–2.45 (1H,
m), 2.03–1.90 (1H, m), and 1.63–1.45 (1H, m, 3,4-CH ).
C
15
H
17
N O. Calculated, m/z: 269.1397.
4
1
(
1-[(2S,5S)-5-(Azidomethyl)pyrrolidin-2-yl]naphthalen-
2-ol (9b). R 0.24 (petroleum ether – Et O – AcOEt,
f
2
1
2
7.5:1.5:1.0). Dark-yellow oil. H NMR spectrum, δ, ppm
(J, Hz): 7.74 (2H, d, J = 9.1, H Ar); 7.64 (1H, d, J = 8.8,
H Ar); 7.46–7.39 (1H, m, H Ar); 7.27 (1H, t, J = 7.7,
H Ar); 7.06 (1H, d, J = 8.9, H Ar); 5.20 (1H, dd, J = 9.7,
J = 6.8, 2'-CH); 3.78–3.68 (1H, m, 5'-CH); 3.63 (1H, dd,
J = 12.4, J = 4.3) and 3.48 (1H, dd, J = 12.4, J = 7.1,
2
N
3
2
1
3
C NMR spectrum, δ, ppm: 168.4; 72.4; 55.2; 37.2; 23.9.
Synthesis of Betti bases 8–11 a,b (General method). To
a solution of imine 4 or 5 (1.0 equiv) in dry CHCl (c 0.2 M),
3
phenolic compound 6 or 7 (1.0 equiv) was added. The
reaction mixture was heated under MW at 120°C for 2 h.
The solvent was evaporated, and the crude residue was
purified by flash chromatography.
CH
2
N ); 2.58–2.46 (1H, m), 2.24–2.12 (1H, m), 2.00–1.84
3
(1H, m), and 1.82–1.68 (1H, m, 3',4'-CH ). OH and NH
2
were not observed. 13C NMR spectrum, δ, ppm: 156.2;
132.1; 129.0; 128.9; 128.3; 126.3; 122.3; 121.0; 120.3;
114.7; 57.7; 56.2; 54.7; 32.9; 28.8. Found, m/z: 269.1395.
1
-((2R,5S)-5-{[(tert-Butyldimethylsilyl)oxy]methyl}-
12
pyrrolidin-2-yl)naphthalen-2-ol (8a).
R
f
0.80 (petroleum
C
15
H
17
N
4
O. Calculated, m/z: 269.1397.
2-[(2R,5S)-5-{[(tert-Butyldimethylsilyl)oxy]methyl}-
pyrrolidin-2-yl)-5-methoxyphenol (10a). R 0.46 (petroleum
ether – AcOEt, 7:3). Dark-yellow oil. H NMR spectrum,
δ, ppm (J, Hz): 6.85 (1H, d, J = 8.3, H Ar); 6.40 (1H, d,
J = 2.6, H Ar); 6.33 (1H, dd, J = 8.3, J = 2.6, H Ar); 4.25
ether – Et O – AcOEt, 7.5:1.5:1.0). Pale-yellow oil.
2
1
H NMR spectrum, δ, ppm (J, Hz): 13.36 (1H, br. s, OH);
f
1
7
7
.76 (1H, d, J = 8.4, H Ar); 7.73 (1H, d, J = 7.6, H Ar);
.64 (1H, d, J = 8.9, H Ar); 7.42 (1H, ddd, J = 8.5, J = 6.8,
J = 1.5, H Ar); 7.27 (1H, ddd, J = 7.9, J = 6.7, J = 1.1,
H Ar); 7.06 (1H, d, J = 8.8, H Ar); 5.14 (1H, t, J = 8.1,
(1H, dd, J = 9.1, J = 7.1, 2'-CH); 3.75 (3H, s, OCH
(1H, dd, J = 9.9, J = 4.6) and 3.57 (1H, dd, J = 9.9, J = 7.2,
CH O); 3.45–3.34 (1H, m, 5'-CH); 2.13–2.02 (1H, m), 1.97–
1.82 (2H, m), and 1.71–1.53 (1H, m, CH ); 0.90 (9H, s,
3
); 3.70
2
'-CH); 3.78 (1H, dd, J = 9.9, J = 4.9) and 3.68 (1H, dd,
J = 9.9, J = 7.3, CH
2
O); 3.56–3.45 (1H, m, 5'-CH); 2.94–
.72 (1H, m, NH); 2.53–2.32 (1H, m), 2.09–1.96 (1H, m),
.94–1.82 (1H, m), and 1.80–1.63 (1H, m, 3',4'-CH ); 0.93
). C NMR
2
2
1
(
2
2
C(CH
3
)
3
); 0.08 (6H, s, 2SiCH ). OH and NH were not
3
1
3
13
9H, s, C(CH
3
)
3
); 0.12 (6H, s, 2SiCH
3
observed. C NMR spectrum, δ, ppm: 159.9; 158.6; 128.3;
spectrum, δ, ppm: 156.3; 132.2; 128.8 (2C); 128.2; 126.2;
118.0; 104.8; 102.3; 67.1; 62.7; 59.7; 55.2; 32.5; 26.5;
1
2
22.2; 121.0; 120.2; 115.5; 67.1; 60.0; 58.4; 31.7; 26.8;
6.0; 18.3; –5.3; –5.4. Found, m/z: 358.2201. C21 Si.
25.9; 18.3; –5.4 (2C). Found, m/z: 338.2154. C18
H
32NO Si.
3
H
32NO
2
Calculated, m/z: 338.2146.
Calculated, m/z: 358.2197.
2-((2S,5S)-5-{[(tert-Butyldimethylsilyl)oxy]methyl}-
pyrrolidin-2-yl)-5-methoxyphenol (10b). R 0.35 (petroleum
ether – AcOEt, 7:3). Dark-yellow oil. H NMR spectrum,
δ, ppm (J, Hz): 6.84 (1H, dd, J = 8.3, J = 2.2, H Ar); 6.39
(1H, d, J = 2.6, H Ar); 6.32 (1H, dd, J = 8.3, J = 2.6, H Ar);
4.34 (1H, dd, J = 9.2, J = 6.4, 2'-CH); 3.75 (3H, s, OCH
3.70–3.58 (1H, m) and 3.55–3.43 (2H, m, CH O, 5'-CH);
2.19–2.05 (1H, m), 2.02–1.83 (2H, m), and 1.63–1.46 (1H,
m, 3',4'-CH ); 0.90 (9H, s, C(CH ); 0.07 (6H, s, 2SiCH ).
1
-((2S,5S)-5-{[(tert-Butyldimethylsilyl)oxy]methyl}-
pyrrolidin-2-yl)naphthalen-2-ol (8b). R 0.48 (petroleum
ether – Et O – AcOEt, 7.5:1.5:1.0). Pale yellow oil.
f
1
f
2
1
H NMR spectrum, δ, ppm (J, Hz): 7.75 (1H, d, J = 8.5,
H Ar); 7.74 (1H, d, J = 8.0, H Ar); 7.64 (1H, d, J = 8.9,
H Ar); 7.42 (1H, ddd, J = 8.4, J = 6.8, J = 1.4, H Ar); 7.30–
.23 (1H, m, H Ar); 7.07 (1H, d, J = 8.9, H Ar); 5.17 (1H,
dd, J = 9.8, J = 6.9, 2'-CH); 3.78–3.69 (1H, m) and 3.68–
3
);
2
7
2
3
)
3
3
13
3
2
1
.56 (2H, m, CH
.43 (1H, m), 2.14–2.00 (1H, m), 1.99–1.82 (1H, m), and
.80–1.65 (1H, m, 3',4'-CH ); 0.93 (9H, s, C(CH ); 0.11
). OH was not observed. C NMR
2
O, 5'-CH); 3.02–2.78 (1H, m, NH); 2.58–
OH and NH were not observed. C NMR spectrum,
δ, ppm: 159.9; 159.2; 128.2; 117.6; 104.7; 102.3; 64.4;
61.0; 58.4; 55.2; 34.0; 26.8; 25.9; 18.2; –5.4 (2C). Found, m/z:
2
)
3 3
1
3
(
6H, s, 2SiCH
3
338.2154. C18
2-[(2R,5S)-5-(Azidomethyl)pyrrolidin-2-yl]-5-methoxy-
phenol (11a). R 0.58 (petroleum ether – AcOEt, 1:1). Dark-
H
32NO
3
Si. Calculated, m/z: 338.2151.
spectrum, δ, ppm: 156.6; 132.2; 128.8 (2C); 128.2; 126.2;
1
2
22.1; 121.0; 120.4; 115.2; 64.3; 58.6; 57.7; 33.2; 27.1;
5.9; 18.3; –5.3; –5.4. Found, m/z: 358.2201. C21 Si.
f
1
H
32NO
2
yellow oil. H NMR spectrum, δ, ppm (J, Hz): 6.84 (1H, d,
J = 8.3, H Ar); 6.40 (1H, d, J = 2.6, H Ar); 6.33 (1H, dd,
J = 8.3, J = 2.5, H Ar); 4.27 (1H, dd, J = 9.4, J = 6.5,
Calculated, m/z: 358.2197.
1
-[(2R,5S)-5-(Azidomethyl)pyrrolidin-2-yl]naphthalen-
2
-ol (9a). R 0.42 (petroleum ether – Et O – AcOEt,
f
2
2'-CH); 3.76 (3H, s, OCH
3
); 3.51–3.35 (3H, m, CH
2
3
N ,
3
32