954
RAZA ET AL.
TABLE 2. Comparison of [α]D of reported and calculated
λmax (log ε) = 328 nm (4.2857); LR EIMS m/z in amu (% abundance): 491
(100) [M]+•, 230 (17) [PhthN – CH(iPr)C ≡ O+, A], 202 (46) [A – CO].
values of 2a-h
(2 S)-9-[2 -(2 -Benzazole-1 ,3 -dione-2 -yl)-4 -methyl
pentanoato]-2-
[α]2D6
d (g/cm3)
[α]2D6
Ad (ee, %)16
benz[d]naphtha[1,2-b]oxine-1-one 10c (colorless needles, 1.9 g, 62%);
mp 200°C, Rf: 0.50 (EtOAc / n-hexane, 1:4); [α]2D2: –36.0 (c 1.0, CHCl3);
1H NMR (400 MHz, CDCl3, δ): 8.48 (1H, d, J = 7.0, H8), 7.95–8.10 (4H,
2
a
A16
Ba
2
e
Ab
Bc
Bd
m, Phth Hs), 7.86 (2H, d, J = 7.8, H11 & H14), 7.75–7.81 (2H, m, H5
&
À23.0
À22.5
À69.0
À23.4
1.265 1.23
1.140 1.10
1.082 1.05
À13.98
(95.6)
À1.44
(97.7)
À31.73
(95.8)
—
À13.80
H6), 7.73 (1H, s, H10), 7.65 (1H, t, J = 7.1 Hz, H7), 7.60 (1H, t, J = 8.5 Hz,
H12), 7.58 (1H, t, J = 7.0 Hz, H13), 5.50 (1H, dd, J = 8.4, 3.5 Hz, H2´), 2.62–
2.87 (1H, m, H4′), 2.16–2.34 (1H, m, Hβ3´), 1.57–1.73 (1H, m, H3α´), 1.04
(6H, d, J = 6.5, H5´ & CH3 at C4´); 13C NMR (100 MHz, CDCl3, δ): 162.3
(2×, C1 & C3 ), 161.0 (C1′), 158.0 (C1), 156.2, 153.6 (C9 & C3), 150.5
(C4a), 144.4 (C6), 134.7 (C10a), 133.2 (2×, C1a & C3a ), 132.0 (2×,
C4 /C5 ), 131.8 (C8), 130.6 (C8a), 128.0 (2×, C4 /C5 ), 127.5, 127.3 (C7
& C5), 126.5, 126.1, 125.7 (C13, C12 & C11), 124.8 (C14a), 123.4 (C14),
122.0 (C10), 115.3 (C4), 61.4 (C2′), 44.1 (C3′), 30.0 (2×, C5′ & CH3 at
C4´), 25.9 (C4′); IR (KBr): ύmax = 1722 cm-1 (bs, C=O); UV-vis (CCl4): λmax
(log ε) = 329 nm (4.0051); LR EIMS m/z in amu (% abundance): 505 (100)
[M]+•, 244 (25) [PhthN–CH(iBu)C ≡ O+, A], 216 (33) [A – CO].
b
c
À69.4
À23.2
f
À1.41
À30.90
À6.85e
g
h
d
À215.7 À214.5
—
1.85
A: Reported values in the literature; B: Calculated values.
aEtOH in 1.0 dm cell.
bDensity of neat and degassed liquids are reported at 20 ºC.
cdensity of neat and degassed liquids are calculated at 34 2 ºC. dneat liquids
in 1.0 dm cell.
eEtOAc in 1.0 dm cell.
(2 S)-9-[2 -(2 -Benzazole-1 ,3 -dione-2 -yl)-3 -phenyl
propanoato]-2-
benz[d]naphtha[1,2-b]oxine-1-one 10d (colorless solid, 2.0 g, 60%); mp
210°C, Rf: 0.55 (EtOAc / n-hexane, 1:4); [α]2D2: –12.0 (c 1.0, CHCl3); 1H
NMR (500 MHz, CDCl3, δ): 8.48 (1H, d, J = 7.0, H8), 7.90–8.10 (4H, m,
Phth Hs), 7.86 (2H, d, J = 7.8, H11 & H14), 7.75–7.81 (2H, m, H5 & H6),
7.73 (1H, s, H10), 7.65 (1H, t, J = 7.1 Hz, H7), 7.60 (1H, t, J = 8.5 Hz, H12),
7.58 (1H, t, J = 7.0 Hz, H13), 7.18–7.35 (5H, m, benzylic Ph), 5.50 (1H,
dd, J = 7.2, 4.0 Hz, H2´), 3.16–3.34 (1H, m, Hβ3´), 2.57–2.73 (1H, m, H3α´);
13C NMR (125 MHz, CDCl3, δ): 161.0 (C1′), 162.3 (2×, C1 & C3 ), 158.0
(C1), 156.2, 153.6 (C3 & C9), 150.5 (C4a), 144.4 (C6), 139.4 (C1′ ),
134.7 (C10a), 134.5 (C6), 133.2 (2×, C1a & C3a ), 132.0 (2×, C4 /C5 ),
131.8 (C8), 130.6 (C8a), 128.8 (2×, C3′ ), 128.3 (C4′ ), 128.0 (2×,
C4 /C5 ), 127.8 (2×, C2′ ), 127.6, 127.5 (C7 & C5), 126.7, 126.1, 125.5
(C13, C12 & C11), 124.9 (C14a), 123.4 (C14), 122.0 (C10), 110.0 (C4),
61.3 (C2′), 28.4 (C3′); IR (KBr): ύmax = 1735 cm-1 (bs, C=O); UV-vis
(CCl4): λmax (log ε) = 340 nm (3.9568); LR EIMS m/z in amu (% abun-
dance): 539 (100) [M]+•, 278 (10) [PhthN–CH(Ph)C ≡ O+, A], 250 (46)
[A – CO].
TABLE 3. UV and IR absorbance in 10a-f
λmax (nm)
log εa
ύb
MP
(ºC)
10
C=O
a
b
c
d
e
f
159
143
200
210
230
218
142
180
333 (4.3615)
328 (4.2857)
329 (4.0051)
340 (3.9568)
323 (3.2655)
329 (3.9258)
328 (3.2655)
329 (3.2672)
1730
1724
1722
1735
1751
1749
1747
1739
g
h
aL.cm–1.M–1
.
bcm–1
.
(2 S)-9-(2 -Chloropropanoato)-2-benz[d]naphtha[1,2-b]
oxine-1-one
10e (colorless solid, 1.25 g, 70%); mp 230°C, Rf: 0.60 (EtOAc / n-hexane,
1:4); [α]2D2: +3.3 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3, δ): 8.69 (1H, d,
J = 7.8, H8), 8.50 (1H, d, J = 7.8, H5), 7.90 (2H, d, J = 8.0, H11 & H14), 7.84
(1H, t, J = 7.8 Hz, H6), 7.78 (1H, s, H10), 7.64 (1H, t, J = 7.3 Hz, H7), 7.60
(1H, t, J = 7.5 Hz, H12), 7.55 (1H, t, J = 7.3 Hz, H13), 4.96 (1H, q,
J = 6.7 Hz, H2´), 2.01 (3H, d, J = 6.8 Hz, H3´); 13C NMR (100 MHz, CDCl3,
δ): 168.1, 160.0 (C1′ & C1), 148.6, 150.2 (C3 & C9), 137.5 (C4a), 134.1
(C6), 133.8 (C10a), 131.6 (C8), 130.0 (C8a), 127.1, 127.0 (C7 & C5),
126.7, 126.1, 125.7 (C13, C12 & C11), 125.3 (C14a), 119.0 (C14), 115.3
(C4), 110.0 (C10), 73.0 (C2′), 25.4 (C3′); IR (KBr): ύmax = 1751 (bs,
C=O), 702 cm-1 (C–Cl); UV-vis (CCl4): λmax (log ε) = 323 nm (3.2655); LR
EIMS m/z in amu (% abundance): 354, 352 (35, 100) [M]+•, 93, 91 (8,
23) [ClCH(Me)C ≡ O+, A], 65, 63 (15, 43) [A – CO].
(2 S)-9-(2 -Chloro-3 -methylbutanoato)-2-benz[d]naphtha [1,2-b] oxine-
1-one 10f (colorless solid, 1.32 g, 74%); mp 218°C, Rf: 0.57 (EtOAc / n-
hexane, 1:4); [α]2D2: +17.0 (c 1.0, CHCl3); 1H NMR (500 MHz, CDCl3, δ):
8.60 (1H, d, J = 7.6, H8), 8.49 (1H, d, J = 8.0, H5), 7.90 (2H, d, J = 8.0, H11
and H14), 7.83 (1H, t, J = 8.0 Hz, H6), 7.78 (1H, s, H10), 7.64 (1H, t,
J = 7.9 Hz, H7), 7.58 (1H, t, J = 7.9 Hz, H12), 7.55 (1H, t, J = 7.0 Hz, H13),
127.6 (2×, C4 /C5 ), 127.1, 127.0 (C5 & C7), 126.6, 126.5, 125.7 (C13, C12
& C11), 123.5 (C14a), 119.0 (C14), 116.2 (C10), 115.3 (C4), 53.0 (C2′),
14.4 (C3′); IR (KBr): ύmax = 1730 cm-1 (bs, C=O); UV-vis (CCl4): λmax (log
ε) = 333 nm (4.3615); LR EIMS m/z in amu (% abundance): 463 (100)
[M]+•, 202 (12) [PhthN–CH(Me)C ≡ O+, A], 174 (40) [A – CO].
(2 S)-9-[2 -(2 -Benzazole-1 ,3 -dione-2 -yl)-3 -methyl butanoato]-2-benz[d]
naphtha[1,2-b]oxine-1-one 10b (colorless needles, 2.0 g, 70%); mp 143°C, Rf:
0.48 (EtOAc / n-hexane, 1:4); [α]2D2: –10.0 (c 1.0, CHCl3); 1H NMR (500 MHz,
CDCl3, δ): 8.50 (1H, d, J = 7.0, H8), 8.15–7.90 (4H, m, Phth Hs), 7.85 (2H, d,
J = 7.8, H11 & H14), 7.78–7.80 (2H, m, H5 & H6), 7.74 (1H, s, H10), 7.66 (1H, t,
J = 7.1 Hz, H7), 7.60 (1H, t, J = 8.5 Hz, H12), 7.58 (1H, t, J = 7.8 Hz, H13), 5.54
(1H, d, J = 7.3 Hz, H2´), 2.48–2.53 (1H, m, H3′), 1.04 (6H, d, J = 6.5, H4´ & CH3
at C3´); 13C NMR (125 MHz, CDCl3, δ): 168.8 (C1′), 168.3 (2×, C1 & C3 ),
165.0 (C1), 155.0, 152.6 (C9 & C3), 147.5 (C4a), 140.4 (C6), 134.7 (C10a),
134.5 (2×, C1a & C3a ), 133.5 (2×, C4 /C5 ), 131.9 (C8), 130.0 (C8a), 128.0
(2×, C4 /C5 ), 127.5, 127.0 (C7 & C5), 126.5, 126.1, 125.7 (C13, C12 & C11),
121.5 (C14a), 120.0 (C14), 129.2 (C10), 117.3 (C4), 79.0 (C2′), 26.3 (C3′), 16.8
(2×, C4´& CH3 at C3´); IR (KBr): ύmax = 1724 cm-1 (bd s, C=O); UV-vis (CCl4):
Fig. 1. The comparative BB of 10e and 10 g (left) and comparative 1H-NMR of aromatic region of 10c and 10e (right).
Chirality DOI 10.1002/chir