Synthetic studies towards ryanodine

Deslongchamps, Pierre

doi:10.1351/pac197749091329

Cited by 19 publications

(8 citation statements)

References 17 publications

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“…30). 6 Alkylation of methoxyphenol aldehyde 26 with dimethylsulfate gave dimethoxyaldehyde 31, which was then converted into dimethoxyacetal32 by acetalization.…”

Section: Synthesis Of Compounds Of Typementioning

confidence: 99%

“…This work was published in a preliminary form (4) and we now wish to report our investigation in detail. In Part I (this paper), we explain our general synthetic strategy (5,6) and describe the preliminary experiments leading to the discovery of a very convenient unsymmetrical diene, which was needed for the construction of a key tricyclic intermediate via a Diels-Alder cycloaddition. Parts 11-IV describe the remaining work (see accompanying papers).…”

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The total synthesis of (+)-ryanodol. Part I. General strategy and search for a convenient diene for the construction of a key tricyclic intermediate

Deslongchamps¹,

Bélanger²,

Berney³

et al. 1990

Can. J. Chem.

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This paper reports a retrosynthetic analysis that led to the conception of a synthetic strategy for the construction of ryanodol(2). The preparation of a key diene, i.e., spirolactone dienone 47 (19 + 31 -, 33 + 48 + 49 + 52 + 47). and its Diels-Alder reaction with methyl vinyl ketone are reported.Key words: strategy, synthesis, ryanodol, diterpene.PIERRE DESLONGCHAMPS, A N D R~ B~L A N G E R , DANIEL J. F. BERNEY, HANS-JUERG BORSCHBERG, ROBERT BROUSSEAU, ALAIN DOUTHEAU, ROBERT DURAND, HAJIME KATAYAMA, RICHARD LAPALME, DOMINIQUE M. LETURC, CHUN-CHEN LIAO, FREDERICK N. MACLACHLAN, JEAN-PIERRE MAFFRAND, FABRIZIO MARAZZA, ROBERT MARTINO, CLAUDE MOREAU, LUC RUEST, LOUISELLE SAINT-LAURENT, ROGER SAINTONGE et PIERRE SOUCY Can. J . Chem. 68, 115 (1990).On rapporte l'analyse rCtrosynthCtique qui a conduit a la conception d'une strattgie menant a la synthkse du ryanodol(2). On dkcrit la synthkse du dikne-clC, la spirolactone diCnone 47 (19+ 31 + 33+ 48+ 4 9 4 52-47), et sa rCaction de Diels-Alder avec la mtthylvinylcCtone.Mots cles : stratkgie, synthkse, ryanodol, diterpkne.Ryanodine (I), a natural product isolated from Ryania speciosa Vahl, is the ester of pyrrole a-carboxylic acid and the complex diterpene (+)-ryanodol(2) (1) (Scheme 1). The structure of ryanodine including its absolute configuration was elucidated by Wiesner et al. at the University of New Brunswick (2). This work constitutes one of the most brilliant accomplishments in structure elucidation using chemical degradation, and remains a classic piece. The X-ray analysis of thep-bromobenzyl ether 3 of ryanodol was carried out by Srivastava and Przybylska (3). The original assignment of Wiesner was confirmed except for a minor point; the X-ray analysis revealed that the configuration of the isopropyl and tertiary hydroxyl groups at C2 had to be reversed and is as indicated in structures 1-3. ' We completed a total synthesis of (+)-ryanodol in 1979. This work was published in a preliminary form (4) and we now wish to report our investigation in detail. In Part I (this paper), we explain our general synthetic strategy (5, 6) and describe the preliminary experiments leading to the discovery of a very convenient unsymmetrical diene, which was needed for the construction of a key tricyclic intermediate via a Diels-Alder cycloaddition. Parts 11-IV describe the remaining work (see accompanying papers). General strategyRyanodol, a C20H3208 compound, is a pentacyclic diterpene, which has a ring skeleton consisting of 14 carbons and one oxygen atom. Thus, four rings (A, B, C, and E) are carbocyclic whereas the fifth one (ring D) contains an oxygen atom. There is an isopropyl group as well as a tertiary methyl group in ring A, a tertiary methyl group in ring B, and an equatorially oriented secondary methyl group in ring C. In addition, there are five tertiary hydroxyl groups, one of which is part of a hemi-ketal function at one of the junctions of ring D and ring E (cf. C15), and two secondary hydroxyl groups, one in ring A (a-oriented) and one in ring C (a-oriented...

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“…30). 6 Alkylation of methoxyphenol aldehyde 26 with dimethylsulfate gave dimethoxyaldehyde 31, which was then converted into dimethoxyacetal32 by acetalization.…”

Section: Synthesis Of Compounds Of Typementioning

confidence: 99%

mentioning

confidence: 99%

The total synthesis of (+)-ryanodol. Part I. General strategy and search for a convenient diene for the construction of a key tricyclic intermediate

Deslongchamps¹,

Bélanger²,

Berney³

et al. 1990

Can. J. Chem.

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“…Symposium of Natural Products, New Zealand, August 1976 (see ref. 2 (8) to the o-spirolactone dienone 10 (mp 97-98"C, 2 95x yield). d-Carvone (4) was reduced (Pt/H,, ether) (9) to the dihydro derivative 11 which was then oxidized (0,, CH3COOC,H5; Pd/C-H,) to yield the aldehyde carboxylic acid 12.…”

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Total synthesis of ryanodol

Bélanger¹,

Berney²,

Borschberg³

et al. 1979

Can. J. Chem.

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“…Metallocarboranes, reactions, 341 Metabolism, D-fructose, 23 secondary, 377 Micellar catalysis, inhibition, 191 MO and mol states, 74 MO calen, benzenes, 169 CO, CS double bonds, 192 MO following, 344 MO theory, 360 Móbius-Hückel treatment, 344 Molecular states and orbitals, 74 Monolayers, photochem, 188 Mutasynthesis, antibiotics, 214 Natural products, [207][208][209][210][211][212][213][214][215][216][217] marine, 255, [312][313][314][315][316] 13C NMR, 274 polyketide, synth, 260 of Porifera, 155 sulfur, [172][173][174][175][176][177] synthesis, 140 synth from carbohydrates, 206 Nitration, mechanism, 165 Nitration, side reaens in synth, 244 Nitroso cmpds, electrophilic, 96 Nitrosation, amino acids in environment, 136 NMR, cyclic monoenes, 93 deuterium, 58,163 dynamic, 161 lanthanide shift effect, 283 lanthanide shift reagents, 60 organotin cmpds, 162 spin lattice relaxation, 215 NMR, 13C biopolymers, 276 biosynthetic studies, 275 electronic struct, …”

mentioning

confidence: 99%

“…Resolution, optical strategies, 265 RNA, transfer in protein synth, 257 Rubber, vulcanization, 319 Ryanodine, synth, 213 Sandwich cmpds, 61 Selenium dioxide oxidn, 154 Silicon cmpds, anionic rearr, 38 d-orbitals, 375 /j-functionalized, 19 by hydrosilylation, 225,338 Silylated enolates in synth, 241 Smoke, tobacco, nitrogen cmpds, 87 Solid state, organic, topochem, 54 Spin relaxation I3C NMR, 278 Spin-spin coupling, indirect 13C NMR, 280 Stenhouse salts, use, 253 Stereodifferentiating reactions, 373 Stereochemistry, classical foundations, 281 Stereochemistry, heterocycles, 367 Stereochemistry, mass spectrometry, 282 metal redn ketones, 197 Steric effects, ketones, 196 P ligands in organometallics, 88 quant model, 167 Steric interactions, substituents, 69 Steroids, biochem, 379 crystal structure, 285 heterocyclic, 133 uncommon marine, 316 Strain energy modelling, crowded ketones,…”

mentioning

confidence: 99%

Recent Reviews

1978

J. Org. Chem.

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Synthetic studies towards ryanodine

Abstract: -This paper describes the work carried out toward the total synthesis of ryanodine.

Cited by 19 publications

References 17 publications

The total synthesis of (+)-ryanodol. Part I. General strategy and search for a convenient diene for the construction of a key tricyclic intermediate

The total synthesis of (+)-ryanodol. Part I. General strategy and search for a convenient diene for the construction of a key tricyclic intermediate

Total synthesis of ryanodol

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