Studies on the Alkaloids of Fumariaceous Plants I

Tani, Chiaki; Takao, Narao

doi:10.1248/yakushi1947.82.4_594

Cited by 19 publications

(7 citation statements)

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“…Considerable effort has already been directed toward the total synthesis of the naturally occurring BC cis-fused hexahydrobenzo[c]phenanthridine alkaloids. The first synthesis of (±)chelidonine (7) was executed by using the intramolecular Diels-Alder reaction of an o-quinodimethane derived from a benzocyclobutene.11 More recently, the photocyclization of enamides was exploited during a total synthesis of (i)-corynoline (1), (±)-12-hydroxycorynoline (8), and (±)-11 -epicorynoline (9).12 Significant work has also been done on the chemical transformation of certain 13-methylprotoberberine alkaloids to analogues of the naturally occurring cis-13-methylbenzophenanthridines.13 Other analogues of corynoline (1) have been prepared from homophthalimide derivatives.14 However, very little work has been reported on the total synthesis of the naturally occurring BC trans-fused alkaloid 14-epicorynoline (3). We recently reported a total synthesis of (i)-chelidonine (7) that was based on the…”

Section: Discussionmentioning

confidence: 99%

“…We have employed flash photolytic techniques to measure the quantum yields for NO photodissociation from nitrosylferroheme model compounds and the rate constant for NO binding to the five-coordinate FeIIPP(l-MeIm).1 Comparisons between results for model compounds and those for hemoproteins are particularly useful in examining the mechanisms by which the properties of the heme group are modulated by a protein environment.2"4 The binding of NO by ferrohemoproteins is anomalous in a number of respects. Although cooperatively is shown in the binding of (1) Abbreviations: FePP, ferrous protoporphyrin(IX); l-Melm, 1-methylimidazole; Hb, hemoglobin; T, low affinity; R, high affinity; Mb, myoglobin; CTAB, cetyltrimethylammonium bromide; L, diatomic ligand; B, nitrogenous base.…”

mentioning

confidence: 99%

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Nitric oxide ferrohemes: kinetics of formation and photodissociation quantum yields

Rose¹,

Hoffman²

1983

J. Am. Chem. Soc.

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10.9). Air Oxidation of Hydroquinone 29 to Quinone 27. A 15-mg sample of 29 partially air oxidized over the course of -1 month. Purification of 29 (1 g of SO2: solvent I) provided a small sample of pure 27: R, (solvent I) 0.28; NMR (CDCI,) 6 1.16 (t, 3 H, CH2CH3, J = 7 Hz), 2.00 (s, 3 H, CH,), 2.0 (masked m, 2 H, NCH2CH2), 2.31 (ddd, 1 H, = 8, 8, 17 Hz), 3.62 (m, 2 H, NCH2), 4.01 (s, 3 H, OCH,), 4.06 (q, 2 H, CH2CH,), 8.7 (br, 1 H, NH); IR (neat) 3325, 1675, 1661, 1650, 1591, 1573 cm-l.Metal-Catalyzed Cyclization of Hydroquinone 29 to Indoloquinone 16. To a stirred solution of 29 (8.0 mg, 0.02 mmol) in acetonitrile (0.42 mL) were added K2C03 (9.0 mg, 0.6 mmol, 320 mol %) and CuBr2 (1:O mg, 0.005 mmol, 20 mol %). Oxidation to purple 27 was seen within minutes. After 1 1 h the yellow mixture was filtered and evaporated. The residue was dissolved in chloroform, filtered, and evaporated to give 16 as a yellow solid (6.3 mg, 98%). identical with the material prepared above.Metal-Catalyzed Cyclization of Hydroquinone 28 to Indoloquinone 30. The above reaction was repeated on the same scale using hydroquinone 28. Isolation after 4.5 h gave 30: 6.3 mg (98%), mp 157-159 OC; R, (solvent I) 0.56; R, (column A, solvent G, 2 mL/min) 23.7; NMR NCHZCHZCHH, J = 8,8,17 Hz), 2.62 (ddd, 1 H, NCH2CH2CHH, J (CDCI,) 1.38 (t, 3 H, CH2CH3, J = 7.1 Hz), 2.01 (s, 3 H, CHS), 2.60(tt, 2 H, NCH,CH2), 3.12 (t, 2 H, NCH2CH2CH2, J = 7.6), 3.97 (s, 3 Addition of Vinylogous Carbamate 25 to Quinone 7 in the Presence of Copper. Ring Closure to Indoloquinone 3 Esters 16 and 30. To a rapidly stirred solution of 7 (50 mg, 0.16 mmol) and 25 (25 mg, 0.16 mmol) in acetonitrile (2 mL) were added K2C03 (78 mg, 0.56 mmol, 350 mol %), and CuBr2 (3.6 mg, 0.016 mmol, 10 mol %). After 5 days, the mixture was filtered and evaporated to a yellow solid (50 mg, 102%). NMR (CDCIJ analysis showed 16 and 30 in a ratio of 5/95. Preparative MPLC (solvent H) of 10 mg of the mixture gave base-line separation of 16 and 30 and a recovery of 9 mg of 30.Registry No. Mg(02CC-H z C O~C~H S )~, 37517-78-5; 2-methoxy-3-methylhydroquinone, 1760-80-1; 2,3-dibromo-5-methoxy-6-methylhydroquinone, 77357-50-7; homoproline ethyl ester acetate salt, 72866-98-9; 4-aminobutyric acid, 56-12-2.Abstract: The quantum yield for N O photodissociation from iron protoporphyrin 1-methylimidazole nitrosyl, FePP( I-MeIm)(NO), in the presence of excess 1-MeIm is wavelength independent, = 0.08-0.1, and the NO binding rate to the five-coordinate heme, Fe(PP)(l-MeIm), is kSNo = 1.7 & 0.7 X lo8 M-I s-l; for Fe(PP)(NO), = 0.05-0.08. This quantum yield is much higher than believed earlier but nevertheless appears to be significantly less than unity; the result is important to an understanding of heme-ligand photodissociation. In contrast for myoglobin and Tand R-state hemoglobin, k5 = 1.8 X lo7 M-' s-l a nd = lo-,. The observations for model systems and proteins (and comparable results for CO) can be understood self-consistently within a scheme for ligand binding and photorelease that incorporates as an int...

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Section: Discussionmentioning

confidence: 99%

mentioning

confidence: 99%

Nitric oxide ferrohemes: kinetics of formation and photodissociation quantum yields

Rose¹,

Hoffman²

1983

J. Am. Chem. Soc.

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“…Papaveraceae: Argemone ( 52) Glaucium (31) Hypecoum (92) Papaver (75) 33. DIHYDROCHELIRUBINE UV: (EtOH) 227 MS: 349 (100), 348 (80), 347 (6), 333 (6), 332 (7), 318 (6), 305 (1), 304. ( 5), 290(9X315) Sources:…”

Section: (15x22)unclassified

“…Papaveraceae: Bocconia (156, 159) Hunnemannia (170) Rutaceae: Fagara (2,29,74,192,193) Toddalia ( 230) UV: (EtOH) 228 (4.53), 284 (4.67), 320 sh (4.18); Xmm 252 (4.18) (318) See also 170. IR: 2850, 2780, 1460, 1335, 944, 723 (318) 'H-NMR: (CDC13) (170) See also 313, 318. MS: 393 (M+, 12), 348 (100), 347 (1), 333 (6), 332 (7), 318(6), 305 (1), 304 (5), 290 (12) (315) See also 170, 247.…”

Section: Angolinementioning

confidence: 99%

The Benzophenanthridine Alkaloids

Krane¹,

Fagbule²,

Shamma³

et al. 1984

J. Nat. Prod.

247

113

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“…(±)-corynoline (2) (14-15), (±)-6p-methylcorynoline (3) ( 16), (±)-6a-methylcorynoline (4) ( 16), (±)-corynolamine (5) ( 16), (±)-6a-acetonylcorynoline (6) ( 5), (±)-6a-vinylcorynoline (7) ( 5), (±)-6ß-^1 ^ 1 (8) ( 5), ( + )-l4-epicorynoline (9) (17)(18)(19), ( + )-acetylchelidonine(1-Ac)( 20), (±)-acetylcorynoline(2-Ac)( 21), (±)acetyl-6ß-methylcorynoline (3-Ac) ( 5), (±)-acetyl-6a-methylcorynoline (4-Ac) ( 5), (±)-11-0-acetylcorynolamine (5-Ac) ( 16), (±)-diacetylcorynolamine (5-diAc) ( 16), (±)-acetyl-6a-acetonylcorynoline (6-Ac) ( 22), (±)-acetyl-6a-vinylcorynoline (7-Ac) (5), (±)-acetyl-6a-vinylcorynoline (8-Ac) (5), and (+ )-acetyl-14-epicorynoline (9-Ac) (21). Compounds 1, 2, 5, 9, 2-Ac, and 9-Ac are natural products, while the remaining substances are synthetically derived.…”

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confidence: 99%

Reinvestigation of the Conformations of a Variety of Hexahydrobenzo[c]phenanthridine Alkaloids by 470 MHz Pmr and 50 MHz Cmr Spectroscopy

Cushman¹,

Abbaspour²,

Iwasa³

et al. 1984

J. Nat. Prod.

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The high resolution pmr and cmr spectra of a variety of benzo[c]phenanthridine alkaloids and their CF3COOD salts were examined. The chemical shift of H-14 was found to be a reliable indicator of the orientation of the N-methyl group. The conformations of the C rings were assigned on the basis of the coupling constants between H-11 and the two H-12 protons. On the basis of the pmr spectra of (+)-14-epicorynoline (9) and (+/-)-14-epicorynoline-6,6,12 alpha-d3 (13), a revision of certain previous C ring conformations is indicated.

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Studies on the Alkaloids of Fumariaceous Plants I

Cited by 19 publications

References 0 publications

Nitric oxide ferrohemes: kinetics of formation and photodissociation quantum yields

Nitric oxide ferrohemes: kinetics of formation and photodissociation quantum yields

The Benzophenanthridine Alkaloids

Reinvestigation of the Conformations of a Variety of Hexahydrobenzo[c]phenanthridine Alkaloids by 470 MHz Pmr and 50 MHz Cmr Spectroscopy

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