5. Chiroptical properties of compounds containing CDO groups |
215 |
O
H
H H
+0.30 (402), −17.90 (317)2 4 8
O
R1
H
R2
H
R3 
H
|
|
O |
|
R1 |
|
|
AcO |
|
|
R2 |
|
R1 = R3 = H, R2 = CH3 |
18α-H |
|
|
|
18β-H |
R1 |
= H, R2 = CH3 , R3 = OAc |
18α-H |
|
|
18β-H |
R1 |
= R3 = H, R2 = CH2 OAc |
18α-H |
|
|
18β-H |
R1 |
= OAc, R2 = CH2 OAc, R3 = H |
18α-H |
|
|
18β-H |
O
H
H
−2.70 (382), +16.79 (315)2 4 8
R1 R2 R3
H OH O = −2.78(369), −8.74(289), +2.28(263)
OH OH OH −5.36(345), +4.41(277), −4.17(228)
OH H OH −5.17(347), +4.84(278), −3.25(230)
H O = OH −3.27(368), +3.97(271)2 4 9
H
COOCH3
R3
∆ε λ(n → π ) |
∆ε |
λ(π → π ) |
|
−0.15 |
353 |
+3.45 |
242 |
+0.17 |
362 |
−1.15 |
246 |
−1.27 |
339 |
+1.50 |
255 |
+0.56 |
336 |
−1.47 |
253 |
−1.84 |
337 |
+2.80 |
247 |
+0.18 |
362 |
−2.90 |
248 |
−1.45 |
337 |
+3.23 |
245 |
+0.20 |
361 |
−2.05 |
2462 50 |
O
|
H |
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O |
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O |
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O |
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OAc |
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AcO |
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18α-H +0.05 (393), −0.98 (342), +0.95 (265), −3.90 (237) |
−1.3 |
(346), −2.9 (331), |
|||
18β-H |
−0.08 (347) |
−3.48 (246) |
2 50 |
−3.1 |
(319), −10.2 (235)2 51 |
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216 |
Stefan E. Boiadjiev and David A. Lightner |
|||
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OH |
|
H |
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H |
H |
O |
O |
O |
O |
O |
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O |
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O |
O |
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O |
|
−0.68 (317), +9.70 (238)2 52 |
−1.41 (320), +8.22 (238)2 52 |
−0.67 (306), +7.03 (240)2 52 |
||
|
OAc |
|
|
OAc |
H |
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H |
|
O |
OCOC4 H7 |
O |
OR |
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H |
|
O |
OAc |
|
O |
OAc |
|
O |
|
|
O |
+1.38 (330), −9.87 (234)2 52 |
|
R = COC(CH3 ) CHCH3 + 2.54 (299), −3.64 (213)2 53 |
||
|
|
|
R = H |
+1.48 (301), −1.03 (212)2 53 |
|
|
|
R = COPh |
+2.40 (300), −2.68 (227)2 53 |
|
OH |
|
|
O |
|
O |
|
RO |
|
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O |
|
OAc |
|
H |
|
H |
|
|
O |
|
O |
|
+1.42 (430), −6.15 (342), |
R = H +2.58 (450), −2.21 (380), |
|||
−6.39 (329), +2.13 (270)2 54 |
−4.79 (333), −4.42 (318) |
|||
|
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|
R = Ac −1.15 (450), −0.62 (330), |
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+13.62 (273), −3.08 (242)2 54 |
|
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OH |
CH2 OH |
|
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|
HO |
|
R2 |
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|
R1 |
|
|
|
R1 = H, R2 = CH3 |
|
O |
−0.30 (390), −2.77 (304), |
|
H |
+5.84 (283), −1.68 (232) |
|
R1 = CH3 , R2 = H |
||
O |
||
−1.80 (390), −4.51 (305), |
||
OH |
||
+6.41 (284), +6.51 (270)2 55 |
|
|
|
5. Chiroptical properties of compounds containing CDO groups |
217 |
|||
|
|
|
OH |
CH2 OH |
|
OH |
CH2 OH |
|
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|
HO |
R2 |
HO |
|
R2 |
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R1 |
|
R1 |
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O |
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O |
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H |
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H |
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O |
|
H |
O |
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H |
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O |
|
O |
|
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|
|
R1 = H, R2 = CH3 |
R1 = H, R2 = CH3 |
|
||
+3.76 (443), −1.22 (398), +1.31 (350), |
+1.09 (460), −3.11 (420), |
||||||
+3.43 (301), +4.49 (280) |
|
+4.20 (347), +2.10 (279) |
|||||
|
|
|
R1 = CH3 , R2 = H |
R1 = CH3 , R2 = H |
|
||
+2.94 (446), −0.82 (398), +0.65 (360), |
+0.42 (460), −2.35 (420), |
||||||
−1.71 (328), +3.84 (298), +3.02 (281)2 55 |
+2.02 (352), +1.01 (298)2 55 |
||||||
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OAc |
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|
OH |
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O |
|
O |
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O |
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O |
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|
OH |
|
|
OCHO |
|
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|
H |
|
H |
|
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|
|
OH |
|
OHCOCH2 |
OH |
|
+0.43 (380), −0.55 (325), +8.79 (259), |
−1.08 (340), +20.0 (242)2 56 |
||||||
−0.42 (242), +1.29 (234)2 56 |
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OH |
|
H |
O |
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O |
|
O |
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O |
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OAc |
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H |
|
H |
|
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|
OH |
|
COOCH2 |
O |
|
|
|
|
|
||||
−0.20 (420), +7.20 (252), |
+2.11 (445), −2.21 (370), −7.34 (336), |
||||||
+7.20 (232)2 56 |
−6.73 (320), −3.12 (257)2 57 |
|
|||||
218 |
Stefan E. Boiadjiev and David A. Lightner |
|
|
|
OMe |
AcOCH2 |
OH |
|
HO |
|
|
H |
O |
O |
|
|
|
H |
|
HOCH2 |
|
|
AcOCH2 |
+0.82 (320), −1.44 (272)2 57 |
−0.46 (324), +1.54 (292)2 57 |
||
|
|
|
CO2 CH3 |
|
|
|
• |
O |
|
|
|
HO |
|
|
|
|
−0.5 (434), +1.0 (375), −1.1 (261)2 58 |
||
|
R |
|
|
O |
|
R |
|
|
|
||
|
|
|
|
|
OH |
O |
|
HO |
|
|
R |
R = H |
−0.6 (434), +1.0 (373), |
R = CH3 +0.62 (326) |
|
R = bond |
−1.0 (263), +0.2 (240) |
R = Ph +1.24 (345), −9.88 (280)2 59 |
|
−2.1 (434), +1.8 (368), |
|
||
−2.2 (263), +1.9 (241)2 58
|
H |
|
O |
O |
|
R |
|
R = CH3 +0.23 (325) |
−0.38 (325), +3.42 (243)2 6 0 ,2 6 1 |
R = Ph +0.55 (335), −2.45 (275)2 59 |
|
5. Chiroptical properties of compounds containing CDO groups |
219 |
R
R
Ph
R = H
R = Cl
R = Ph
R = 4-CH3 C6 H4
R = 4-CH3 OC6 H4
R = 4-FC6 H4
R = 4-ClC6 H4
R = 4-BrC6 H4
R = 4-pyridyl
O
+0.83 (344) +0.41 (338) −1.46 (364) −1.80 (364) −2.60 (362) −1.53 (365) −1.78 (366) −2.08 (355)
−0.87 (372)2 6 2
Cl
R = H
R = Ph
R = 2-ClC6 H4
R = 2-BrC6 H4
R = 4-ClC6 H4
R = 4-BrC6 H4
R = 2-CH3 C6 H4 R = 2-CH3 OC6 H4 R = 4-CH3 C6 H4
O |
O |
+0.22 (334)2 6 3 |
−0.57 (334)2 6 5 |
+1.57 (340)2 6 5 +1.50 (342)2 6 3 +1.00 (344)2 6 3 +1.68 (343)2 6 3 +1.69 (345)2 6 3 −25 (275)2 6 4 +0.97 (352)2 6 5 +0.73 (362)2 6 5 +1.76 (349)2 6 5
O
|
OCO |
|
X |
|
|
|
|
|
|
|
OCO |
O |
Cl |
|
|
|
|
|
|
+0.69 (345)2 6 3 |
X = H |
+0.85 (333), +6.10 (270) |
|
|
|
X = 4-Cl |
+0.52 (343), +5.30 (266) |
|
|
X = 2,6-Cl2 |
+0.42 (345), +3.90 (258)2 6 6 |
|
O |
|
|
|
|
|
O |
|
H |
|
|
|
|
|
Cl |
|
|
|
H |
|
Cl |
|
|
+1.60 (348), −41.2 (278)2 6 7 |
−1.50 (389), −11.2 (297)2 6 7 |
||
220 |
|
Stefan E. Boiadjiev and David A. Lightner |
|
||||||
|
|
O |
H |
|
|
|
O |
H |
|
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||
O |
|
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|
R1 |
O |
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||||
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||||
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H |
R2 |
|
|
|
H |
R |
|
|
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|
|
|
|
|
||
|
|
R1 = CO2 H, R2 = H |
|
|
|
R = CO2 H |
|
||
|
|
−0.86 (369), |
−1.04 (352), |
|
|
−2.31 (356), −0.08 (271) |
|||
|
|
+0.68 (267), +1.85 (232) |
|
|
+8.80 (238), −4.02 (215) |
||||
|
|
R1 = CH3 , R2 = OH |
|
|
|
R = CH2 OH |
|
||
|
|
−0.95 (372), −2.14 (338) |
|
|
−2.98 (360), −0.97 (261) |
||||
|
|
-1.07 (257), +1.39 (226)2 6 8 |
+5.73 (228)2 6 8 |
|
|||||
MeO |
|
|
|
MeO |
|
|
|||
|
|
|
|
NHCOCH3 |
|
|
|
|
NHCOCH3 |
MeO |
|
|
|
MeO |
|
|
|||
|
|
OMe |
|
|
|
|
OMe |
|
|
|
|
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|
O |
|
|
|
|
OMe |
|
|
|
OMe |
|
|
|
|
O |
|
|
|
(100) |
|
|
|
|
(101) |
|
|
−9.26 (351), −8.21 (274), +11.0 (232) |
−13.1 (345), +2.31 (257), +13.5 (238) |
||||||||
MeO
NHCOCH3
MeO
OMe 
H
H
O
OCH3
(102)
+13.5 (350), −49.6 (293), −15.9 (212)
The CD spectra of approximately fifty alkaloids of colchicine (100) and isocolchicine (101) types and alkaloids with altered tropolone rings (e.g. 102) have been reported269. Six to seven CD bands of these alkaloids were identified in the 400 190 nm region. The 350 nm Cotton effect appears to result from a ! Ł transition of methoxytropone system. The pH-dependent changes in the CD spectra were studied following ionization of a free phenolic group on ring A, a hydroxy group on the tropolone ring or substituted amino group in colchicine (100) analogues270.
5. Chiroptical properties of compounds containing CDO groups |
221 |
O
O
|
|
AcO |
O |
|
|
|
|
AcO |
O |
|
|
|
|
−0.36 (333), +0.51 (294), |
|
O |
|
|
|
+8.23 (233)176 |
|
|
|
|
|
|
|
|
OR |
|
|
|
|
|
3′ |
RO |
3 |
|
|
|
|
|
P |
|
|
|
|
|
O |
|
|
|
|
|
|
|
|
|
|
|
(3S, 3′S)-Astaxanthin R = H |
−3.2 (521), +6.7 (384), −23.1 (323), |
|||
|
|
|
+12.5 (280), −14.4 (249), +12.8 (224)2 71,2 72 |
||
|
|
R = Ac |
+4.5 (387), −19.6 (321), +12.1 (278), |
||
|
|
|
−14.7 (248)2 71 |
|
|
|
|
R = CH3 (CH2 )14 CO +3.7 (385), −16.4 (320), |
|
||
|
|
|
+11.5 (279), −13.0 (248)2 71 |
||
|
|
|
O |
|
O |
HO |
P |
P |
|
HO |
P |
|
|
HO |
|
|
|
|
O |
O |
|
O |
|
+2.0 (285), +5.0 (225)2 73 |
−2.1 (380), +10.9 (316), |
+1.5 (300), −1.0 (270), |
|||
|
|
−7.0 (278), +6.9 (246)2 72 |
+3.5 (250), −0.5 (240), |
||
+7.0 (225)2 73
|
OH |
|
P |
O |
|
+2.5 |
(345), −7.5 (295), |
+4.5 |
(258)2 73 |
222 |
Stefan E. Boiadjiev and David A. Lightner |
O |
O |
HO |
OH |
+6.3 (477), −24.0 (380), +9.0 (305), −8.0 (266)2 71
O
OH
HO
O
−5.9 (466), +7.5 (365), −25.5 (282)2 71
|
|
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|
|
R1 |
|
|
|
Ph |
|
|
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|
|
|
|
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|
O |
|
|
NH C |
R3 |
O |
N |
O |
N |
|||||||
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R2 |
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|
CO2 Me |
|
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|
|
(103) |
|
|
|
(104) |
|
(105) |
||
|
|
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|
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|
|
|
+28.0 (289)2 74 |
|
−16.1 (286)2 74 |
|
R1 |
|
|
R2 |
R3 |
Reference 274 |
|
|
|
||||||
|
C |
|
|
|
CH |
Me |
H |
−32.5 (274) |
O |
N |
|
||||
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||||||||||||
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|||||||||||||
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||||||||||||
|
Et |
|
|
C |
|
CH |
H |
+27.9 (274) |
|
||||||
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||||||||||||
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|
|
||||||||||||
|
|
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||||||||||
|
C |
|
|
|
CH |
n-Pr |
H |
−25.2 |
(274) |
|
|
Ph |
|||
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|
|
|||||||||||
|
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|
||||||||||||
|
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|||||||||||
|
C |
|
|
|
CH |
Et |
Me |
+1.4 |
(276) |
|
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||||
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||||||||||
|
CH |
|
|
CH2 |
Et |
H |
−16.8 |
(278) |
|
|
|
||||
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|
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|
|
|
||||||||||
|
|
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|
|
|||||||||||
|
n-Pr |
|
|
COOMe |
H |
+17.7 |
(274) |
|
(106) |
|
|||||
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|
+15.0 (292)2 74 |
|
Chromophoric derivatives for the optically transparent amino group, such as dimedone derivatives 103 106, were prepared for assigning the absolute configuration of primary and secondary amines. The vinylogous planar amide chromophore (280 290 nm ! Ł
5. Chiroptical properties of compounds containing CDO groups |
223 |
absorption) shows positive Cotton effects for derivatives possessing the (R) configuration in primary and secondary amines274.
Fluorescamine has been used as a Cottonogenic reagent for secondary amines (forming aminoendione chromophore)275 and for primary amines (forming pyrrolinone chromophore, 107)276 whose in situ CD was directly correlated with the amine absolute configuration.
|
R2 |
|
|
|
R1 |
C R3 |
Amine |
|
|
|
N |
(R)-α-methylbenzylamine |
+5.01 (387), |
−7.29 (275) |
|
(R)-α-(1-naphthyl)ethylamine |
+4.73 (388), |
−8.02 (287) |
|
HO |
|
|||
|
(R)-α-phenyl-l-propylamine |
+5.34 (386), |
−8.95 (270) |
|
|
Ph |
|||
|
(R)-norepinephrine |
+1.55 (385), |
−3.48 (285) |
|
|
O |
(R)-2-aminobutane |
+0.38 (385), |
−0.95 (288) |
|
|
|
|
CO2 H
(107)
Circularly polarized (laser) light is widely used not only to study the absorption properties of enantiomers, but also to generate optically active compounds via enantioselective photochemical process.
|
|
CO2 Me |
|
|
|
OCH3 |
HO |
|
|
|
|
OCH3 |
|
|
H |
|
|
O |
O |
O |
CH3 O |
O |
|
|
|
||||
(+)-(1R,5S)-(108) |
(+)-(1R, 4R,5S)-(109) |
(+)-(4S)-(110) |
|
(−)-(1S,5R)-(111) |
|
+2.5 (350) |
+7.8 (305) |
−0.32 (320) |
|
−2.0 (350) |
|
(calcd from 3.7% ee) |
(calcd from 2% ee) |
(calcd from 1.6% ee) |
(calcd from 1.6% ee) |
||
|
|
|
|
O |
|
O |
||
|
|
R |
R |
R R |
||||
O |
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|
|
|
|
OH |
Ph |
|
H |
MeO2 C |
|
H |
||
(+)-(R)-(112) + 1.02 (353) R = H |
+0.17 |
(319), +0.32 (308) |
R = H +0.13 |
(318), +0.22 (307) |
||||
(44%ee) |
(34%ee) |
|
|
|||||
|
|
|
|
|
|
|
||
R = CH3 |
+0.17 |
(319), +0.34 (305)2 8 0 |
R = CH3 −0.04 |
(318), +0.02 (312), |
||||
(8%ee) |
|
|
|
|
|
(27%ee) −0.03 |
(307), +0.04 (300)2 8 0 |
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224 Stefan E. Boiadjiev and David A. Lightner
Some difficult-to-resolve enones were obtained by enantioselective hydration of 108
and 109277, or laser phototransformation using circularly polarized light on 108, 110,
111278 and 112279.
UV irradiation of a cis bicyclic ˛,ˇ-unsaturated ketone in diethyl (C)-tartrate afforded
trans ketone 113 enriched in the |
( )-enantiomer, |
with an |
estimated |
optical purity |
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of 0.5 |
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1%281. |
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O |
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O |
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O |
H |
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H |
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R |
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R |
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(113) |
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−0.67 (307)2 8 1 |
R = H |
−0.030 |
(350), |
R = H |
−0.030 |
(357) |
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+0.027 |
(327) |
R = CH3 |
−0.016 |
(354), |
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R = CH3 |
−0.052 |
(347), |
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+0.009 |
(310) |
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+0.015 |
(313) |
R = Cl |
−0.043 |
(353)2 8 2 |
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R = CH3 O −0.102 |
(343), |
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−0.041 |
(317)2 8 2 |
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O |
H |
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−0.34 (328), −0.12 (287), |
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−0.49 (252), +2.24 (219)2 8 3 |
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Ph |
H |
Ph |
H |
Ph |
H |
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H |
COPh |
H |
COPh |
H |
COPh |
N |
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O |
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H |
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−4.76 (312), −7.76 (260)2 8 4 |
−4.21 (315), −9.00 (263), −2.86 (322), −6.30 (257), |
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+6.97 (232)2 8 4 |
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+8.31 (235)2 8 5 |
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MeO |
OH |
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OMe |
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OH |
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OH |
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O |
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O |
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(114) |
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(115) |
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+0.65 (305), −1.39 (278)2 8 5 |
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−3.30 (310), +1.05 (246), |
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−1.15 (230)2 8 6 |
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