Morphinandienone alkaloids

Stuart, K. L.

doi:10.1021/cr60269a003

Cited by 43 publications

(31 citation statements)

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“…Much of this attention has been focused on the transformation into morphinandienonetype alkaloids. [138][139][140][141][142][143][144][145][146] In the early studies, the biomimetic phenolic coupling reaction using chemical oxidants or some other synthetic methods such as the Pschorr reaction, photochemical coupling reaction, or benzyne reaction, were continually employed. Despite large efforts, the yields of the coupling step were usually low and, in general, these methodologies did not afford practical routes to morphinandienone alkaloids.…”

Section: Efficient Synthesis Of Morphinandienone Alkaloidmentioning

confidence: 99%

Development and Application of New Oxidation Systems Utilizing Oxometalate Catalysts

Hamamoto

2012

CHEMICAL & PHARMACEUTICAL BULLETIN

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This review describes our recent efforts in the development and application of new oxidation systems utilizing oxometalate catalysts. The novel use of heteropoly acid (HPA), an acidic oxometalate catalyst, in hypervalent iodine-mediated oxidations provided an effective strategy to generate cation radical species that enables a variety of direct C-H functionalizations of aromatic compounds. This strategy brought a facile biaryl synthesis and new spirodienone syntheses in aromatic oxidation chemistry. Moreover, this strategy opens up a facile synthetic route to morphinandienone alkaloids. On the other hand, the use of oxometalate catalyst together with poly(N-isopropylacrylamide) (PNIPAAm)-based polymer in the development of new solid-phase catalyst provided a novel reaction system in water. Due to the characteristic temperature-responsive intelligence of PNIPAAm, this reaction system brought a remarkable acceleration of the reactivity and ease of catalyst recovering in catalytic oxidation that uses hydrogen peroxide or oxygen gas (O 2 ) as primary oxidant. In addition, the recovered solid-phase catalyst could be used for consecutive reactions without any significant loss of its catalytic efficacy.

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Section: Efficient Synthesis Of Morphinandienone Alkaloidmentioning

confidence: 99%

Development and Application of New Oxidation Systems Utilizing Oxometalate Catalysts

Hamamoto

2012

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…In nature it occurs both in optically active and racemic © 1993 International Union of Crystallography REGULAR STRUCTURAL PAPERS 979 forms (Stuart, 1971). Sinoacutine contains a sequence isosteric with y-aminobutyric acid (GABA) and according to in vitro measurements (Kardos, Blask6, Simonyi & Szfintay, 1984) it can be considered as a partial agonist of the GABA/ benzodiazepine receptor complex.…”

Section: Commentmentioning

confidence: 99%

“…Some of the final calculations were performed with PARST (Nardelli, 1983). The scattering factors were those of Cromer & Mann (1968) forms (Stuart, 1971). Sinoacutine contains a sequence isosteric with y-aminobutyric acid (GABA) and according to in vitro measurements (Kardos, Blask6, Simonyi & Szfintay, 1984) it can be considered as a partial agonist of the GABA/ benzodiazepine receptor complex.…”

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confidence: 99%

Structure of sinoacutine

Ribár¹,

Kapor²,

Gašić³

et al. 1993

Acta Crystallogr C

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In the title alkaloid, (9a,13a)-5,6,8,14-tetradehydro-4-hydroxy-3,6-dimethoxy-17-methylmorphinan-7-one, the mean value of three C--N--C angles is 111.0 (4) ° indicating sp 3 hybridization of the N atom.The interplanar angle between the aromatic ring A and planar ring D [maximum deviation 0.051 (5)/~ at C14] is 53.8 (1)°. The absolute configuration has been assigned to agree with the known chirality at C3 (S) [Southon & Buckingham, (1989). Dictionary of Alkaloids, p. 974. London: Chapman and Hall]. CommentSinoacutine is an enantiomer of salutaridine. In nature it occurs both in optically active and racemic © 1993 International Union of Crystallography REGULAR STRUCTURAL PAPERS 979 forms (Stuart, 1971). Sinoacutine contains a sequence isosteric with y-aminobutyric acid (GABA) and according to in vitro measurements (Kardos, Blask6, Simonyi & Szfintay, 1984) it can be considered as a partial agonist of the GABA/ benzodiazepine receptor complex. Sinoacutine plays an important role as biosynthetic intermediate in the formation of morphine (Barton & Cohen, 1957).The title alkaloid of morphinandienone-type was isolated from the aerial parts of the species Corydalis ochroleuca. The extraction of dried plant material was carried out according to Preininger, Vesely, Ga~i6, ~imanek & Dolej~ (1975) and it was isolated as described by Gagi6, Popovi6 & Dragutinovi6 (1985). Total synthesis of sinoacutine has been described by Ludwig & Schaefer (1986).From the puckering parameters (Cremer & Pople, 1975) of ring B [Q = 0.530 (6) .~, ~o = 18.2 (8) °, 0 = 52.6 (6) °] it can be seen that it is a transition form between half-chair and envelope shape, whereas ring C [Q = 0.556 (6) .,~, ~p = 305 (4) °, 0 = 8.6 (6)°], forming a bridge between C ll and the chiral atom C3, adopts an almost perfect chair conformation. HY participates in a symmetrical three-centered hydrogen-bond interaction (Jeffrey, 1978). 1.514 (7) C12--C13 1.328 (6) C3--N 1.475 (7) C13--C14 1.479 (7) C4--C5 1.520 (7) C13--O4 1.371 (6) C5--C61.387 (7) C14--O1 1.214 (6) C5--C101.408 (7) C15--C16 1.521 (7) C6--C71.361 (8) C15--N 1.471 (7) C7--C81.372 (8) C17--O2 1.403 (7) C8--C91.402 (7) C18--O4 1.399 (7) C8--O21.363 (6) C19--N 1.469 (7) C9--C101.387 (6)Data were corrected for Lorentz and polarization factors. A value for Rint is missing since a unique data set was collected. The structure was solved by direct methods using SHELXS86 (Sheldrick, 1985) and refined using SHELX76 (Sheldrick, 1976). The positions of H atoms were generated from assumed geometry except that of H3' which was calculated using the program MMX (Allinger, Scb_~fer, Siam, Klimkowski & van Alsenoy, 1985) and refined isotropically. The positions of H atoms in CH3 groups were checked on a Ap map. Non-H atoms were refined anisotropicaUy. Several weighting schemes were tested and the best results were obtained with the unit weight. The overall isotropic temperature factor for H atoms was U1 = 0.0575 (50) A 2 and for the methyl H atoms U2 = 0.0868 (73) ,~2. Software used to prepare material for...

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“…The chemistry of morphine alkaloids has been reviewed in the past by Holmes [1], Holmes and Stork [2], Stork [3], Stuart [4], Bentley [5], Blaskó and Cordell [6], and Szántay and his co-workers [7]. Some books and book chapters have also been devoted to this topic (Small and Lutz [8], Bentley [9], Ginsburg [10], Hosztafi [11].…”

Section: Introductionmentioning

confidence: 99%

Recent Developments in the Chemistry of Thebaine and its Transformation Products as Pharmacological Targets

Berényi¹,

Csutorás²,

Sipos

2009

CMC

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The most practical synthetic routes to the preparation of as important pharmaceuticals as oxycodone, naloxone, naltrexone, nalbuphine and buprenorphine have utilized the alkaloid, thebaine, as a starting material. This review intends to focus on chemical transformations of morphinans which resulted in morphinandiene derivatives with well-established and novel pharmacological potencies. These chemical transformations were mainly associated with the formation and substitution of the unique diene structure of the ring C of the morphinan backbone.

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Morphinandienone alkaloids

Cited by 43 publications

References 5 publications

Development and Application of New Oxidation Systems Utilizing Oxometalate Catalysts

Development and Application of New Oxidation Systems Utilizing Oxometalate Catalysts

Structure of sinoacutine

Recent Developments in the Chemistry of Thebaine and its Transformation Products as Pharmacological Targets

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