1214 J. Am. Chem. Soc., Vol. 120, No. 6, 1998
Reddy and Sharpless
δ 159.1, 156.5, 136.3, 131.2, 128.5, 128.2, 127.8, 114.1, 113.9,
67.0, 66.3, 56.6, 55.4; HRMS calcd for C17H19NO4 (M + H)+
302.1392, found 302.1382; HPLC Chiralcel AD, 15% i-PrOH/
hexane, 0.7 mL min-1, 254 nm, 14.6 min (S), 22.2 min (R).
(dd, J ) 8.2, 2.0 Hz, 1H), 4.8 (br s, 1H), 3.8 (br s, 2H), 2.0 (br
s, 1H, OH, D2O exchangeable); 13C NMR (100 MHz, CDCl3)
δ 156.0, 140.6, 140.3, 138.6, 136.2, 128.7, 128.4, 128.0, 127.9,
127.2, 127.0, 126.9, 126.3, 66.7, 65.4, 56.8; HRMS calcd for
C22H21NO3 (M + Na)+ 370.1419, found 370.1411; HPLC
Chiralcel AD, 15% i-PrOH/hexane, 0.5 mL min-1, 254 nm, 20.4
min (S), 26.2 min (R).
(1R)-N-(Benzyloxycarbonyl)-1-(4-(benzyloxy)phenyl)-2-hy-
droxyethylamine (ent-3A) [(DHQD)2PHAL]: mp 120-121
°C; [R]25D ) -35.6° (c ) 0.5, 95% EtOH); 1H NMR (400 MHz,
CDCl3) δ 7.4-7.25 (m, 10H), 7.2 (d, J ) 8.7 Hz, 2H), 6.95 (d,
J ) 8.7 Hz, 2H), 5.36 (d, J ) 12.4 Hz, 1H), 5.08 (m, 4H), 4.78
(br, 1H), 3.84 (br s, 2H); 13C NMR (100 MHz, CDCl3) δ 158.4,
156.4, 136.8, 136.2, 128.6, 128.5, 128.2, 128.0, 127.7, 127.4,
115.1, 70.0, 67.0, 66.5, 56.5; HRMS calcd for C23H23NO4 (M
+ Na)+ 400.1525, found 400.1535; HPLC Chiralcel AD, 30%
i-PrOH/hexane, 0.5 mL min-1, 254 nm, 14.0 min (S), 25.8 min
(R).
(1S)-N-(Benzyloxycarbonyl)-1-(3,5-bis(benzyloxy)-4-meth-
oxyphenyl)-2-hydroxyethylamine (5A) [(DHQ)2PHAL]: mp
117-118 °C; [R]25D ) +30.6° (c ) 0.5, 95% EtOH); 1H NMR
(400 MHz, CDCl3) δ 7.42-7.3 (m, 15H), 6.52 (s, 2H), 5.4-
5.36 (br s, 1H), 5.09 (s, 6H), 4.7-4.6 (br s, 1H), 3.9 (s, 3H),
3.8-3.6 (m, 2H), 1.9 (br s, 1H, OH, D2O exchangeable); 13C
NMR (100 MHz, CDCl3) δ 156.3, 152.7, 138.9, 136.9, 136.2,
134.6, 128.5, 128.2 (br), 127.9, 127.4, 106.3, 71.1, 67.0, 66.3,
60.9, 56.9; HRMS calcd for C31H31NO6 (M + Cs)+ 646.1206,
found 646.1187; HPLC Chiralcel AD, 15% i-PrOH/hexane, 0.5
mL min-1, 254 nm, 34.8 min (S), 63.5 min (R).
(1S)-N-(Benzyloxycarbonyl)-1-(4-acetoxyphenyl)-2-hy-
droxyethylamine (10A) [(DHQ)2PHAL]: mp 153-154 °C;
1
[R]25 ) +30.8° (c ) 0.5, 95% EtOH); H NMR (400 MHz,
D
CDCl3) δ 7.3 (m, 5H), 7.24 (d, J ) 8.2 Hz, 2H), 6.68 (d, J )
8.2 Hz, 2H), 5.6 (br s, 1H), 5.07 (dd, J ) 8.2, 20.4 Hz, 2H),
4.7 (br s, 1H), 3.76 (m, 2H), 2.2 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 169.7, 156.3, 150.0, 137.2, 136.2, 128.5, 128.2, 127.7,
121.9, 115.4, 67.0, 66.1, 56.4, 21.1; HRMS calcd for C18H19-
NO5 (M + Na)+ 352.1161, found 352.1167; HPLC Chiralcel
AD, 30% i-PrOH/hexane, 0.5 mL min-1, 254 nm, 10.6 min (S),
13.3 min (R).
(1S)-N-(Benzyloxycarbonyl)-1-((4-(p-toluenesulfonyl)oxy)-
phenyl)-2-hydroxyethylamine (11A) [(DHQ)2PHAL]: mp
143-144 °C; [R]25D ) +24.0° (c ) 0.4, 95% EtOH); 1H NMR
(400 MHz, CDCl3) δ 7.6 (d, J ) 8.3 Hz, 2H), 7.28 (m, 7H),
7.15 (d, J ) 8.4 Hz, 2H), 6.9 (d, J ) 8.3 Hz, 2H), 5.7 (br s,
1H), 5.04 (m, 2H), 4.7 (br s, 1H), 3.74 (m, 2H), 2.4 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 156.3, 148.9, 145.5, 138.5,
132.3, 129.8, 128.5, 128.4, 128.2, 128.1, 127.9, 122.5, 67.1,
65.7, 56.2, 21.7; HRMS calcd for C23H23NO6S (M + Cs)+
574.0300, found 574.0316; HPLC Chiralcel AD, 15% i-PrOH/
hexane, 0.5 mL min-1, 254 nm, 58.3 min (S), 90.6 min (R).
(1S)-N-(Benzyloxycarbonyl)-1-(3,5-dimethoxyphenyl)-2-
hydroxyethylamine (6A) [(DHQ)2PHAL]: mp 109-110 °C;
1
[R]25 ) +32.6° (c ) 0.5, 95% EtOH); H NMR (400 MHz,
D
CDCl3) δ 7.3 (m, 5H), 6.4 (d, J ) 1.9 Hz, 2H), 6.35 (d, J )
1.9 Hz 1H), 5.48 (d, J ) 7.0 Hz, 1H), 5.09 (m, 2H), 4.7 (br s,
1H), 3.89 (m, 2H), 3.75 (s, 6H), 1.8 (br s, 1H, OH, D2O
exchangeable); 13C NMR (100 MHz CDCl3) δ 161.1, 156.4,
141.6, 136.2, 128.5, 128.2, 104.7, 99.5, 67.1, 66.4, 57.2, 55.4;
HRMS calcd for C18H21NO5 (M + Na)+ 354.1317, found
354.1311; HPLC Chiralcel AD, 15% i-PrOH/hexane, 0.5 mL
min-1, 254 nm, 24.1 min (S), 30.0 min (R).
(1S)-N-(Benzyloxycarbonyl)-1-(3-nitrophenyl)-2-hydroxy-
ethylamine (12A) [(DHQ)2PHAL]: mp 85-86 °C; [R]25
)
D
1
+28.6° (c ) 0.5, 95% EtOH); H NMR (400 MHz, CDCl3) δ
8.2 (br s, 1H), 8.13 (d, J ) 8.2 Hz, 1H), 7.64 (d, J ) 8.1 Hz,
1H), 7.5 (t, J ) 8.2, 8.1 Hz, 1H), 7.34 (m, 5H), 5.78 (br s, 1H),
5.09 (m, 2H), 4.9 (br s, 1H), 3.90-3.84 (m, 2H), 2.07 (br s,
1H, OH); 13C NMR (100 MHz, CDCl3) δ 156.3, 148.4, 141.9,
135.0, 133.1, 129.6, 128.6, 128.3, 128.1, 122.7, 121.6, 67.2,
65.4, 56.2; HRMS calcd for C16H16N2O5 (M + Na)+ 339.0957,
found 339.0949; HPLC Chiralcel AD, 15% i-PrOH/hexane, 0.5
mL min-1, 254 nm, 25.2 min (S), 34.2 min (R).
(1R)-N-(Benzyloxycarbonyl)-1-(3,4,5-trimethoxyphenyl)-
2-hydroxyethylamine (ent-7A) [(DHQD)2PHAL]: mp 96-
1
97 °C; [R]25 ) -27.8° (c ) 0.5, 95% EtOH); H NMR (400
D
MHz, CDCl3) δ 7.34 (m, 5H), 6.47 (s, 2H), 5.53 (d, J ) 6.8
Hz, 1H), 5.1 (s, 2H), 4.7 (br s, 1H), 3.85-3.80 (m, 11H), 1.96
(br s, 1H, OH, D2O exchangeable); 13C NMR (100 MHz,
CDCl3) δ 156.4, 153.4, 137.2, 136.2, 135.1, 128.5, 128.2, 103.4,
102.6, 67.0, 66.2, 60.8, 57.2, 56.0; HRMS calcd for C19H23-
NO6 (M + Na)+ 384.1423, found 384.1415; HPLC Chiralcel
AD, 15% i-PrOH/hexane, 0.5 mL min-1, 254 nm, 28.0 min (S),
35.6 min (R).
(1S)-N-(Benzyloxycarbonyl)-1-(4-(trifluoromethyl)phenyl)-
2-hydroxyethylamine (13A) [(DHQ)2PHAL]: mp 142-143
°C; [R]25D ) +18.2° (c ) 0.5, 95% EtOH); 1H NMR (400 MHz,
CDCl3) δ 7.6 (d, J ) 8.1 Hz, 2H), 7.4 (d, J ) 8.1 Hz, 2H), 7.3
(m, 5H), 5.5 (br s, 1H), 5.1 (dd, J ) 11.8, 22.8 Hz, 2H), 4.8 (br
s, 1H), 3.92-3.86 (m, 2H), 1.8 (br s, 1H); 13C NMR (100 MHz,
CDCl3) δ 156.5, 143.9, 129.3, 128.3, 128.0, 127.8, 126.9, 126.3,
125.2, 66.8, 64.9, 56.6; HRMS calcd for C17H16F3NO3 (M +
Na)+ 362.0980, found 362.0988; HPLC Chiralcel AD, 15%
i-PrOH/hexane, 0.5 mL min-1, 254 nm, 12.4 min (S), 23.3 min
(R).
(1S)-N-(Benzyloxycarbonyl)-1-(4-methoxynaphthyl)-2-hy-
droxyethylamine (8A) [(DHQ)2PHAL]: mp 146-147 °C;
1
[R]25 ) +7.75° (c ) 0.5, 95% EtOH); H NMR (400 MHz,
D
CDCl3) δ 8.32 (d, J ) 8.1 Hz, 1H), 8.0 (d, J ) 7.6 Hz, 1H),
7.52 (m, 2H), 7.34 (m, 6H), 6.73 (d, J ) 8.0 Hz, 1H), 5.53 (br
s, 1H), 5.1 (br s, 1H), 3.99-3.90 (br s, 5H), 2.4 (br s, 1H, OH,
D2O exchangeable); 13C NMR (100 MHz, CDCl3) δ 156.5,
155.4, 136.3, 131.6, 128.5, 128.1, 127.1, 126.3, 126.1, 125.3,
123.7, 122.8, 122.5, 103.9, 67.0, 65.7, 55.6, 52.9; HRMS calcd
for C21H21NO4 (M + Na)+ 374.1368, found 374.1360; HPLC
Chiralcel AD, 15% i-PrOH/hexane, 0.5 mL min-1, 254 nm, 20.9
min (S), 26.5 min (R).
(1R)-N-(Benzyloxycarbonyl)-1-(4-cyanophenyl)-2-hy-
droxyethylamine (ent-14A) [(DHQD)2PHAL]: mp 90-91 °C;
1
[R]25 ) -34.8° (c ) 0.5, 95% EtOH); H NMR (400 MHz,
D
CDCl3) δ 7.58 (d, J ) 7.9 Hz, 2H), 7.35 (d, J ) 7.9 Hz, 2H),
7.24 (m, 5H), 5.8 (br s, 1H), 5.0 (m, 2H), 4.8 (br s, 1H), 3.84-
3.76 (m, 2H), 2.4 (br s, 1H, OH); 13C NMR (100 MHz, CDCl3)
δ 156.2, 145.2, 135.9, 132.4, 128.6, 128.4, 128.2, 127.5, 118.6,
111.4, 67.2, 65.4, 56.6; HRMS calcd for C17H16N2O3 (M +
Na)+ 319.1059, found 319.1050; HPLC Chiralcel AD, 15%
i-PrOH/hexane, 0.5 mL min-1, 254 nm, 24.0 min (S), 54.2 min
(R).
(1S)-N-(Benzyloxycarbonyl)-1-(4-biphenyl)-2-hydroxyeth-
ylamine (9A) [(DHQ)2PHAL]: mp 164-165 °C; [R]25
+46.8° (c ) 0.5, 95% EtOH, 80% ee); H NMR (400 MHz,
CDCl3) δ 7.6-7.3 (m, 14H), 5.5 (d, J ) 7.2 Hz, 1H), 5.1
)
D
1
(1S)-N-(Benzyloxycarbonyl)-1-(4-bromophenyl)-2-hy-
droxyethylamine (15A) [(DHQ)2PHAL]: mp 133-134 °C;