The crystal structure and absolute configuration of (−)-dihydroergotamine methanesulfonate monohydrate

Hebert, Hans

doi:10.1107/s0567740879011092

Cited by 17 publications

(4 citation statements)

References 8 publications

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“…is observed. Similar effects were found in, for example, ergotamine (21,22) in a chain of 5 atoms in which the end oxygens were an acceptor and a donor in hydrogen bond formation. The shortening of C(12)-C(13) is significant and reflects similar alternate changes in electron distribution through the N(15)-C(12) -C(13)-C (14) -N(18) chain.…”

supporting

confidence: 56%

The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.0^2,6]heptane, C₁₄H₁₃ClN₂O₄S

Przybylska¹,

Garratt²

1981

Can. J. Chem.

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MARIA PRZYBYLSKA and DENNIS G . GARRATT. Can. J. Chem. 59,658 (1981). l-Chloromethyl-3-endo-(2',4'-dinitrophenylthio)tricyclo[2.2.1.02~6]heptane, C14H,,CIN204S, crystallizes in space group P2,la with unit cell dimensions a = 12.785(2), b = 10.653(1), c = 11.061(1) A, $ = 101.5ql)q Z = 4.The structure was solved from Patterson and Fourier maps. The parameters were refined by block-diagonal least-squares to a final R = 0.038 for 2063 observed reflections. The structural data provide unequivocal proof for our earlier ascertainment of configurational-specific exo attack upon the endocyclic double bond of 2-methylenebicyclo[2.2. Ilhept-5-ene with homoallylic participation.The molecule is characterized by the presence of an interaction between oxygen of the 2-nitro group and a sulphur atom, and of a weak bifurcated hydrogen bond system involving C-H...O bonds. Chem. 59,658(1981). L e chloromtthyl-1 (dinitro-2',4' phknylthio) 3-endo tricycl0

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supporting

confidence: 56%

The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.0^2,6]heptane, C₁₄H₁₃ClN₂O₄S

Przybylska¹,

Garratt²

1981

Can. J. Chem.

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“…Nevertheless, this study provided in principle another example of the potential of N-acyl imines as intermediates in synthetic sequences. Furthermore, the establishment of the structure of the cycloltripeptide 29 by X-ray analysis is noteworthy, since only two other related structures have been determined by X-ray methods (16,17). Considering that in less complex a-azidoketo systems such as 4 a the yield of N-acyl imine derived products is around 45%, this method might prove useful for the generation of carbinolamide ether or dehydro-amino acid (enamide) units of natural products less prone to isomerizations than the diketopiperaziie derivatives reported in this paper…”

Section: Discussionmentioning

confidence: 99%

Photochemistry of 2-azido-2-alkyl-3-oxobutanoic esters and amides

Edwards¹,

Rank²

1990

Can. J. Chem.

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Photolysis of 2-alkyl-2-azido-3-oxobutanoic esters and amides gave products resulting from alkyl or acyl migration onto nitrogen. The resulting ketimimes could be isolated in moderate purity, but the N-acyl imines were rapidly converted into solvation products or enamides (N-acetyl dehydroamino acid esters) resulting from double bond migration. Mechanisms for formation of these products are discussed. The N-(2-azido-2-methyl-3-oxobutanoyl) derivative of the diketopiperazine from L-valyl-L-proline gave a stereoisomer of the cyclol tripeptide unit of ergovaline.Key words: N-acyl imines, mechanism of 2-azido-3-keto ester photolysis, cyclol tripeptide synthesis, ergovaline.OLIVER E. EDWARDS et WERNER RANK. Can. J. Chem. 68, 1425Chem. 68, (1990.La photolyse des esters et des amides des acides 2-alkyl-2-azido-3-oxobutano'iques fournit des produits qui proviennent de migrations d'alkyles ou d'acyles vers l'azote. L'Ctat de puretC des cCtimines qui en rksultent est correct; toutefois, les imines N-acyltes se transforment rapidement en produits de solvatation ou en enamides (esters des N-acCtyl dChydroamino acides) qui rksultent d'une migration de double liaison. On discute des mCcanismes de formation de ces produits. La dCrivC N-(2-azido-2-mtthyl-3-oxobutanoyle) de la dicCtopipCrazine provenant de la L-valyl-L-proline fournit un stCrCoisom&re de l'unitC tripeptide cyclol de l'ergovaline.Mots clPs : imines N-acyltes, mCcanisme de photolyse des esters 2-azido-2-cCto, synthkse de I'unitC trlpeptide cyclol, ergovaline.[Traduit par la revue]

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“…Bindungslän-gen und -winkel bedürfen hinsichtlich ihrer Zahlenwerte keiner besonderen Diskussion, da sie Literaturwerten vergleichbarer Strukturen weitgehend entsprechen. Zum Vergleich können etwa ( -)Dihydroergotamin-Methansulfonat von Hebert (1979) oder zwei Ergolin-Derivate einer italienischen Autorengruppe (Foresti Serantoni et al, 1977und 1980 herangezogen werden. Allerdings ist zu beachten, daß bei allen bisher publizierten Strukturen C(2)-C(3) als Doppelbindung mit einem Abstand von 1.33-1.36 Â vorlag, während bei dem hier untersuchten 2,3-Dihydroergolin-Derivat diese Bindung eine Einfachbindung mit einer Länge von ca.…”

Section: Ergebnisse A) Molekül-und Kristallstrukturunclassified

Struktur des Ergolinderivats 1,1-Diethyl-3-[(2R,3R,5R,8S,10S)-2,3-dihydro-2,6- dimethyI-8-ergolinyl]-harnstoff bei drei verschiedenen Temperaturen: 295 K, 50 Κ und 15 Κ

Luger¹,

Zöbel²

1993

Zeitschrift Für Kristallographie - Crystalline Materials

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Crystal structure ¡ Ergotine derivative / X-ray diffraction at 295/50115 Κ / Temperature factorsAbstract. The structure of the ergoline derivative l,l-Diethyl-3-[(2R,3R,5R,8S,10S)-2,3-dihydro-2,6-dimethyl-8-ergolinyl]-urea has been determined by X-ray single crystal diffraction at three temperatures: 295, 50 and 15 K. Large displacement parameters of the diethyl-urea side group atoms cause rather improper bond distances at room temperaturewhich, after cooling, adopt normal values. An inspection of the displacement parameters expressed in U eq 's, shows that even the temperature reduction from 50 to 15 Κ causes an average decrease of t/ eq 's by 33%. At room temperature, the individual displacement parameters depend strongly on the atomic distances from the molecular center of gravity. This dependence disappears almost completely at 15 K.

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The crystal structure and absolute configuration of (−)-dihydroergotamine methanesulfonate monohydrate

Cited by 17 publications

References 8 publications

The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.0^2,6]heptane, C₁₄H₁₃ClN₂O₄S

The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.0^2,6]heptane, C₁₄H₁₃ClN₂O₄S

Photochemistry of 2-azido-2-alkyl-3-oxobutanoic esters and amides

Struktur des Ergolinderivats 1,1-Diethyl-3-[(2R,3R,5R,8S,10S)-2,3-dihydro-2,6- dimethyI-8-ergolinyl]-harnstoff bei drei verschiedenen Temperaturen: 295 K, 50 Κ und 15 Κ

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The crystal structure and absolute configuration of (−)-dihydroergotamine methanesulfonate monohydrate

Cited by 17 publications

References 8 publications

The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.02,6]heptane, C14H13ClN2O4S

The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.02,6]heptane, C14H13ClN2O4S

Photochemistry of 2-azido-2-alkyl-3-oxobutanoic esters and amides

Struktur des Ergolinderivats 1,1-Diethyl-3-[(2R,3R,5R,8S,10S)-2,3-dihydro-2,6- dimethyI-8-ergolinyl]-harnstoff bei drei verschiedenen Temperaturen: 295 K, 50 Κ und 15 Κ

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The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.0^2,6]heptane, C₁₄H₁₃ClN₂O₄S

The addition of 2,4-dinitrobenzenesulphenyl chloride to 2-methylenebicyclo[2.2.1]hept-5-ene: the crystal structure of 1-chloromethyl-3-endo-(2′,4′-dinitrophenylthio)tricyclo[2.2.1.0^2,6]heptane, C₁₄H₁₃ClN₂O₄S