Prostaglandins. I. Direct synthesis of optically active Corey-intermediate from (S)-(-)-malic acid

Paul, Kalidas; Johnson, Francis; Favara, D.

doi:10.1021/ja00421a052

Cited by 42 publications

(4 citation statements)

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“…Paul et al 10 ) and successfully applied it to the preparation of the key intermediate 7 in JA syntheses. Using compound 7 four JA homologues with n-alkyl substituents at C-2 position were prepared efficiently.…”

Section: Discussionmentioning

confidence: 99%

Syntheses of Jasmonic Acid Related Compounds and Their Structure-Activity Relationships on the Growth of Rice Seedings

Yamane¹,

Sugawara²,

Suzuki³

et al. 1980

Agricultural and Biological Chemistry

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Section: Discussionmentioning

confidence: 99%

Syntheses of Jasmonic Acid Related Compounds and Their Structure-Activity Relationships on the Growth of Rice Seedings

Yamane¹,

Sugawara²,

Suzuki³

et al. 1980

Agricultural and Biological Chemistry

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“…(g) After 1 h at 80 °C a solution of the (chloromethyl-D-norvincadifformine 16 in dimethylformamide containing some water showed, by TLC, primarily 14a-hydroxyvincadifformine (8b), traces of the hydroxymethyl compound 10, and some material with R¡ 0. For 14/3-hydroxyvincadifformine (8a): TLC R¡ 0.43 (silica, 2% methanol in dichloromethane); NMR (CDC13) 8.95 (s, 1 H), 6.80-7.22 (m, 4 ), 3.90 (brs, 1 H), 3.77 (s, 3 ), 0.90-2.30 (m, 14 ), 0.60 (t, 3 H); IR (CHC13) ¡w 3600,3380,3005,2970,2940 Tabersonine (1). (a)15 A solution of 140 mg (0.40 mmol) of 14/3-hydroxyvincadifformine (8a) and 125 mg (0.48 mmol) of triphenylphosphine in 0.5 mL of acetonitrile was heated at 80 °C for 5 min.…”

Section: Methodsmentioning

confidence: 99%

“…The organic solution was washed three times with 10 mL of 50% aqueous NaHC03, twice with 10 mL of water, and once with 10 mL of brine, dried over MgS04, filtered, and concentrated to 4.12 gofa yellow oil. The crude product was purified by chromatography on 150 g of silica (hexanes/ether, 3:2) to yield 3.04 g (76%) of the methyl esters: R¡ 0.78 (silica; hexanes/ether, 3:2); IR (film) 2960, 2870,1730,1455,1435,1385,1315,1265,1200,1115,980,840,800,735 cm™1; NMR (CDC13) 0.90 (t, J = 6 Hz, 3 ), 1.20-2.80 (m, 5 H), 3.64 (s, 3 ), 3.64-4.16 (m, 3 H); mass spectrum (80 eV), m/e 212. Epimeric 4,.…”

Section: Methodsmentioning

confidence: 99%

“…Tabersonine ( 1) and the C-20 epimeric pandolines (2a,b) are biogenetically derived from either of two respective postulated isomeric precursors, the dehydrosecodines 3 and 4.1,2 Formation of the pentacyclic alkaloids 1 and 2 is a consequence of intramolecular addition of the first dienamine double bond in the dehydrosecodines (3,4) to the indoloacrylate moiety. However, through an alternative intramolecular Diels-Alder reaction of the dienamine and acrylate functions, a dehydrosecodine can also be expected to cyclize to an isoquinuclidine product, i.e., catharanthine (5, Scheme I).…”

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confidence: 99%

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Studies in biomimetic alkaloid syntheses. 8. Total syntheses of the C-14 epimeric hydroxyvincadifformines, tabersonine, a (hydroxymethyl)-D-norvincadifformine and the C-20 epimeric pandolines

Kuehne¹,

Okuniewicz²,

KIRKEMO³

et al. 1982

J. Org. Chem.

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Condensation of methyl l,2,3,4,5,6-hexahydroazepino[4,5-b]indole-5-carboxylate (6) with 5-chloro-2-ethyl-4hydroxypentanal lactol ( 14) yielded the 14a-and 14/3-hydroxyvincadifformines (8a,b) in an epimeric ratio which was solvent dependent. On condensation of the indoloazepine 6 with 4,5-epoxy-2-ethylpentanal (9) the same compounds were formed together with a (hydroxymethyl)-D-norvincadifformine, 10, as the major product.Dehydration of 14d-hydroxyvincadifformine (8a) readily gave tabersonine (1), while 14a-hydroxyvincadifformine (8b) could only be dehydrated by carbamate pyrolysis. The latter compound (8b) and the (hydroxymethyl)-D-norvincadifformine 10 could be converted to vincadifformine (18) through the chloromethyl derivative 16. Condensation of the indoloazepine 6 with the epimeric 4,5-dichloro-2-ethylpentanals ( 19) also gave the (chloromethyl)-D-norvincadifformine 16 and 14/3-chlorovincadifformine (20). Dehydrohalogenation of the latter compound provided a third sequence to tabersonine (1). A synthesis of the C-20 epimeric pandolines (2a,b) from 5-chloro-4-ethyl-4-hydroxypentanal lactol ( 22) similarly allowed control of the C-20 epimeric product ratio through its solvent dependence.

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Prostaglandins

Collins¹

2000

Kirk-Othmer Encyclopedia of Chemical Technology

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Prostaglandins are a family of naturally occurring substances found in animals and humans. They are produced from 20 carbon fatty acids in vivo and play important and diverse roles in both health and disease. Unlike circulating hormones, prostaglandins are synthesized and released by most tissues, act near their site of synthesis, and then are rapidly inactivated by metabolic enzymes. They are among the most potent substances known and exert regulatory influences on virtually all tissues and organs. Because of their diverse biological effects and their potential as therapeutic agents, prostaglandins underwent intense scrutiny following their structural elucidation and availability in the early 1960s. Both academic and industrial laboratories studied their biosynthesis, metabolism, physiological and pharmacological effects, and their chemical and physical properties. The total synthesis of prostaglandins presented formidable challenges. Because of their structural and stereochemical complexity and chemical instability, they provided a strong impetus to the development of new synthetic methodologies. The prostaglandins and many analogues are available by total synthesis and some have reached the marketplace as therapeutic agents. Examples are prostaglandin E 1 (PGE 1 ), used in cardiovascular and reproductive indications; analogues of prostaglandin F 2 α , used in estrus synchronization in farm animals; misoprostol, an analogue of PGE 1 , used in the treatment of ulcers; prostacyclin and some of its analogues, used for cardiovascular diseases; and latanoprost, used in the treatment of glaucoma.

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Prostaglandins. I. Direct synthesis of optically active Corey-intermediate from (S)-(-)-malic acid

Cited by 42 publications

References 1 publication

Syntheses of Jasmonic Acid Related Compounds and Their Structure-Activity Relationships on the Growth of Rice Seedings

Syntheses of Jasmonic Acid Related Compounds and Their Structure-Activity Relationships on the Growth of Rice Seedings

Studies in biomimetic alkaloid syntheses. 8. Total syntheses of the C-14 epimeric hydroxyvincadifformines, tabersonine, a (hydroxymethyl)-D-norvincadifformine and the C-20 epimeric pandolines

Prostaglandins

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