Synthetic studies on lycoricidine and related compounds. II. Total synthesis of (.+-.)-lycoricidine.

Ohta, Shunsaku; Kimoto, Shoshichiro

doi:10.1248/cpb.24.2977

Cited by 47 publications

(27 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The preparation of aminoconduritol 202, possessing all four stereocenters in the structure of narciclasine with the correct relative and absolute stereochemistries, is accomplished by the asymmetric cycloaddition the chloronitroso compound 200 with diene 201, followed by the reductive N-O cleavage with Al-Hg (Scheme 18). 200 is derived from ketopinic acid (199,65 USD/1 gram, Aldrich). Although the starting material is somewhat expensive, ketoester 203 is isolated by simple extraction of the aqueous reaction mixture in 93% yield and can be recycled.…”

Section: Synthesis Of (+)-Narciclasine By Yan and Coworkersmentioning

confidence: 99%

Chemistry, Biology, and Medicinal Potential of Narciclasine and its Congeners

2008

View full text Add to dashboard Cite

Ornamental flower growers know that placing a cut daffodil (a.k.a. narcissus) in a vase with other flowers has a negative effect on the quality of those flowers and significantly shortens their vase life. Furthermore, a common horticultural practice for the cultivation of narcissus flowers involves the introduction of cuts on the bulbs before immersing them into water. The mucilage that leaches out from the cuts is constantly removed by frequent changing of water and this leads to sprouting. These observations raise speculation that specific components in the mucilage of the narcissus bulbs may have powerful growth-inhibitory effects. Historical use of narcissus flowers, as well as at least thirty other plants of the Amaryllidaceae family, in folk medicine for the management of cancer 1 speaks volumes to validate this conjecture. Indeed, powerful anticancer properties of Narcissus poeticus L. were already known to the Father of Medicine, Hippokrates of Kos (ca. B.C. 460-370), who recommended a pessary prepared from narcissus oil for the treatment of uterine tumors. 2 His successors, the ancient Greek physicians Pedanius Dioscorides (ca. A.D. 40-90) and Soranus of Ephesus (A.D. 98-138) continued using this therapy in the first and second centuries A.D.3 , 4 In addition, the topical anticancer uses of extracts from this plant5 , 6 as well as from N. pseudonarcissus7-9 were recorded in the first century A.D. by the Roman natural philosopher Gaius Plinius Secundus, (A.D. 23-79), better known as Pliny the Elder. 10 Even the Bible provides multiple references to the Mediterranean N. tazetta L., which has a long history of use against cancer. 11 The applications of narcissus oil in cancer management continued in the middle ages in Chinese, North African, Central American and Arabian medicine. 1,12 The uses of other genera of the Amaryllidaceae family were also common, e. g. Hymenocallis caribaea (L. emend Gawler) Herbert, utilized by early European medical practitioners for inflammatory tumors. 13 More recently, the plants of the Amaryllidaceae have been under intense scrutiny for the presence of the specific metabolites responsible for the medicinal properties associated with this plant family. The study began in 1877 with the isolation of alkaloid lycorine from Narcissus pseudonarcissus 14 and since then more than 100 alkaloids, exhibiting diverse biological activities, have been isolated from the Amaryllidaceae plants. Based on the present scientific evidence, it is likely that isocarbostyril constituents of the Amaryllidaceae, such as narciclasine, pancratistatin and their congeners, are the most

show abstract

Section: Synthesis Of (+)-Narciclasine By Yan and Coworkersmentioning

confidence: 99%

Chemistry, Biology, and Medicinal Potential of Narciclasine and its Congeners

2008

View full text Add to dashboard Cite

show abstract

“…[9] Racemic 2 was first synthesised by Ohta and Kimoto in 1976 as an advanced intermediate in the total synthesis of another hydroxylated phenanthridone, lycoricidine. [15] A few years later, enantiopure 2 was prepared for the first time by Paulsen and Stubbe as an intermediate in their synthesis of Abstract: The stereocontrolled synthesis of (+)-7-deoxypancratistatin is described. The convergent synthesis has been achieved by two different strategies, both of which commence from a pentose and piperonal.…”

Section: Introductionmentioning

confidence: 99%

“…[ [15][16][17][18][19][20][21] Most notable are the synthesis by Hudlickys group and the second-generation synthesis by Keck and co-workers. Hudlickys group used a whole-cell biooxidation of bromobenzene as the first step to afford (1 S,2 S)-3-bromocyclohexa-3,5-diene-1,2-diol, which was then converted into 2 by way of a total of ten linear steps in 3.0 % overall yield.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 7‐Deoxypancratistatin from Carbohydrates by the Use of Olefin Metathesis

Håkansson

Palmelund

Holm

et al. 2006

Chemistry A European J

View full text Add to dashboard Cite

The stereocontrolled synthesis of (+)-7-deoxypancratistatin is described. The convergent synthesis has been achieved by two different strategies, both of which commence from a pentose and piperonal. The latter is converted into allylic bromide 7, which is then coupled with a protected methyl 5-deoxy-5-iodo-D-ribofuranoside in the presence of zinc metal. The first strategy involves a total of only 13 steps from D-ribose and piperonal, but suffers from a low yield in the zinc-mediated reaction between ribofuranoside 9, benzylamine, and bromide 7. The second strategy involves a total of 18 steps from D-xylose and piperonal. The former is converted into ribofuranoside 28, which is coupled with bromide 7 in the presence of zinc, and this is followed by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation, and deprotection then affords the natural product.

show abstract

“…Diels-Alder cycloaddition has been proposed several times to construct the C-ring [10, [149][150][151][152][153]. A short report on the synthesis of an advanced intermediate toward lycoricidine based on the construction of the C-ring using a Diels-Alder approach and subsequent functionalization of the cyclohexene ring has been proposed by Mehta [154].…”

Section: Iii-3-1) Formation Of the 10a-10b Bondmentioning

confidence: 99%

“…The latter are prepared by cyclization of 2-aryl-cyclohexenyl isocyanates under boron trifluoroetherate catalysis [175]. This approach was used in one of the early syntheses of lycoricidine [150]. Two phenanthridin-6(5H)-ones 252 and 255 were obtained from isocyanates 251 and 254, respectively.…”

Section: Iii-4) Synthetic Analogsmentioning

confidence: 99%

Chemistry and Synthesis of Highly Oxygenated Alkaloids from Amaryllidaceae: Lycoricidine, Narciclasine, Pancratistatin and Analogs

Chapleur¹,

Chrétien²,

Ahmed³

et al. 2006

COS

View full text Add to dashboard Cite

Plants of the genus Amaryllidaceae produce a number of alkaloids and other non-basic related molecules, some of them showing antitumor activities. The low availability of these often-complex structures, coupled with their interesting biological properties, has stimulated a long-standing interest in the chemistry community. Total syntheses of challenging structures such as lycoricidine, narciclasine and pancratistatin, which are highly oxygenated tetracyclic systems comprising up to six contiguous chiral centers on ring C, have been accomplished. These well-known structures, more than thirty years for lycoricidine, continue to stimulate interest in synthetic work to provide enough synthetic material or analogs, and also are a model target to test or develop new synthetic methodologies. The synthetic studies around these complex phenanthridinones made use of the latest up-to-date synthetic methodologies and led to the development of novel methods of functionalization and carbon-carbon bond formation. The purpose of this review is to summarize recent total syntheses and synthetic approaches towards these three highly oxygenated members of this particular class of alkaloids over the last twenty years. The review is arranged according to the different strategies used for the construction of the benzophenanthridinone ring system.

show abstract

Synthetic studies on lycoricidine and related compounds. II. Total synthesis of (.+-.)-lycoricidine.

Cited by 47 publications

References 0 publications

Chemistry, Biology, and Medicinal Potential of Narciclasine and its Congeners

Chemistry, Biology, and Medicinal Potential of Narciclasine and its Congeners

Synthesis of 7‐Deoxypancratistatin from Carbohydrates by the Use of Olefin Metathesis

Chemistry and Synthesis of Highly Oxygenated Alkaloids from Amaryllidaceae: Lycoricidine, Narciclasine, Pancratistatin and Analogs

Contact Info

Product

Resources

About