An Overview of the Total Synthesis of Pyrrolizidine Alkaloids via [4 + 1]Azide-Diene Annulation Methodology

Hudlický, Tomáš; Seoane, Gustavo; Price, John D.; Gadamasetti, Kumar

doi:10.1055/s-1990-21120

Cited by 40 publications

(17 citation statements)

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“…Ring Opening of Endocyclic Vinylaziridine 7. The chemistry of vinylaziridines has been confined for the most part to their use in rearrangement sequences leading to functionalized pyrrolines. − The lack of data concerning the nucleophilic opening of vinylaziridines with carbon nucleophiles surprised us, in view of the expected similarity of such systems to the well-studied vinyloxiranes. , There were no disclosures of corresponding trends for vinylaziridines prior to our preliminary report on parallel reactivities of vinyloxiranes and vinylaziridines with organometallic reagents . Recently, several papers have appeared describing the interaction of cuprates and other organometallics with acyclic vinylaziridines …”

Section: Resultsmentioning

confidence: 99%

Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents¹

et al. 1996

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Whole-cell biooxidation of bromobenzene with Pseudomonas putida 39D or the recombinant Escherichia coli JM109 (pDTG601) yields (1S,2S)-3-bromocyclohexa-3,5-diene-1,2-diol (9a), which is protected as the acetonide and converted to vinylaziridines 7, 15a, 63, and 64. Our route to (+)-pancratistatin features the coupling of a higher order cyanocuprate (derived by ortho-metalation from N,N-dimethyl-2-[(tert-butyldimethylsilyl)oxy]-3,4-(methylenedioxy)benzamide) with aziridine 7 to generate 28, which contains the carbon framework of the title alkaloid. Functional group manipulations resulted in the preparation of epoxydiol 50, which was transformed in a unique fashion and under mild conditions (H2O/PhCO2Na) to (+)-pancratistatin, thus completing a concise synthesis of (+)-pancratistatin in 14 steps from bromobenzene (2% overall yield). To improve this first generation attempt, a new route was devised utilizing carbomethoxyaziridine 64 and its coupling to the cuprate of 3,4-(methylenedioxy)bromobenzene. The adduct was converted to (+)-7-deoxypancratistatin in a total of 11 steps from bromobenzene (3% overall yield), and the basis for further improvement toward a practical synthesis of pancratistatin-type alkaloids was formulated.

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Section: Resultsmentioning

confidence: 99%

Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents¹

et al. 1996

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“…[141][142][143][144][145][146][147][148][149][150][151] Several total syntheses of racemic pyrrolizidine and indolizidine alkaloids were accomplished in this way. [141][142][143][144][146][147][148][149][150] The enantiodivergent syntheses of trihydroxyheliotridane 6,7-O-acetonide 36 was possible via the chiral azidodiene 35, both enantiomers of which were available from L-and D-erythrose (Scheme 25). 145 A sequence starting from L-glutamic acid and involving the homochiral azidodiene 37 allowed access to (-)-8a-epidesacetoxyslaframine 38 (Scheme 26…”

Section: Intramolecular Cycloadditions Of Alkadienyl Azidesmentioning

confidence: 99%

Pyrrolizidine and Indolizidine Syntheses Involving 1,3-Dipolar Cycloadditions

Broggini¹

1999

Synthesis

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“…The pyrrolizidine subgroup includes a number of naturally occurring alkaloids, many of which exhibit useful activities as glycosidase inhibitors as well as antiviral and anticancer agents. [144][145][146] In spite of these remarkable biological applications, only a few reports dealing with the design and implementation of totally chemical approaches to hydroxylated pyrrolizidines have appeared during the period covered by this article. Most syntheses in this area have used pentoses or hexoses as chiral sources while employing extensive manipulation of functional groups.…”

Section: B Bicyclic Compounds 1 Pyrrolizidine Derivativesmentioning

confidence: 99%

Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool

Casiraghi¹,

Zanardi²,

Rassu³

et al. 1995

Chem. Rev.

185

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Casiraghi et al.Giovanni Casiraghi was born in Monza, Italy, in 1939 and took his laurea degree in Chemistry in the University of Pavia. After postdoctoral work at the same University with Professor S. Pietra (1965Pietra ( -1968), he joined the Department of Organic Chemistry at University of Parma. In 1971 he became an Assistant Professor and in 1980 an Associate Professor of Organic Chemistry. In 1986 he was promoted to a Professorship in Organic Chemistry and, in the same year, he transferred to the University of Sassari. In 1991 he returned to the University of Parma, joining the Faculty of Pharmacy (Pharmaceutical Department) where he was appointed to the Chair in Organic Chemistry. Topics he is now interested in include asymmetric organic synthesis and the design and implementation of novel synthetic strategies to densely functionalized compounds of biological interest, including carbohydrate mimics, amino acids, modified nucleosides, glyco-and nucleoporphyrins.Franca Zanardi was born in S. Secondo, Parma, Italy, in 1968. She studied Chemistry at the University of Parma where she received her laurea degree in 1993. Since 1992 she has been working under the OBn OBn 19 20 21 3 Key: (a) MeN02, DBU; (b) Net oxidation; (c) EtSH, HCI; then NaH, BnBr, DMF; then Mel, Na2C03; (d) (Et0)2P(0)CH(NHCbz)C02Me, NaH, CH2CI2; (e) H2, Pd/C; (f) H2, Pd(OH)2; then Dowex H*. MeOH. 3 Key: (a) HCN2C02Et; (b) Ao20, pyridine; then Rh2(AcO)4; (c) NH2NH2, MeOH; (d) Mn02, CHCI3; then TBAF, THF; (e) MCPBA, CHCI3;then AcOH; then NH4OH; (f) Rh2(AcO)4, C6H6; (g) TFA; then NH4OH.

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An Overview of the Total Synthesis of Pyrrolizidine Alkaloids via [4 + 1]Azide-Diene Annulation Methodology

Cited by 40 publications

References 0 publications

Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents¹

Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents¹

Pyrrolizidine and Indolizidine Syntheses Involving 1,3-Dipolar Cycloadditions

Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool

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An Overview of the Total Synthesis of Pyrrolizidine Alkaloids via [4 + 1]Azide-Diene Annulation Methodology

Cited by 40 publications

References 0 publications

Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents1

Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents1

Pyrrolizidine and Indolizidine Syntheses Involving 1,3-Dipolar Cycloadditions

Stereoselective Approaches to Bioactive Carbohydrates and Alkaloids-With a Focus on Recent Syntheses Drawing from the Chiral Pool

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Product

Resources

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Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents¹

Toluene Dioxygenase-Mediated cis-Dihydroxylation of Aromatics in Enantioselective Synthesis. Asymmetric Total Syntheses of Pancratistatin and 7-Deoxypancratistatin, Promising Antitumor Agents¹