Synthesis of erythrina and related alkaloids. 17. Total synthesis of dl-coccuvinine and dl-coccolinine

Abstract

This paper is dedicated to Dr. 0. E. (Ted) Edwards TAKEHIRO SANO, JUN TODA, NOBUTERU MAEHARA, and YOSHISUKE TSUDA. Can. J. Chem. 65,94 (1987).Total synthesis of dl-coccuvinine l a and dl-coccolinine 2a, "abnormal-type" erythrinan alkaloids lacking the C(16) 0-function at the aromatic ring, was effectively achieved by using the Diels-Alder reaction of dioxopyrroline. Isoquinolinopyrrolinedione 6a, a key dienophile, was synthesized via the tetrahydroisoquinoline 5a, which was prepared by BischlerNapieralski cyclization of the arnide 4 a at the unactivated position. The Diels-Alder adduct 7 a of 1,3-bis(trimethylsily1oxy)-butadiene with 6 a with converted stereoselectively into these alkaloids in short steps.

Reactions of fused pyrrole-2,3-diones with binucleophiles

“…[1][2][3][4][5] Until the early nineties these annulated pyrrolediones were studied almost exclusively as subjects for photoreduction and photocyclisation, or as dienophiles in Diels-Alder reactions (for the production of intermediate compounds in the synthesis of alkaloids). A large number of these studies were performed by a certain groups of investigators.…”

Synthesis and chemical transformations of 2,3-dihydropyrrole-2,3-diones annelated on the [a] side by azaheterocycles. (Review)

“…Their reactions with nucleophilic reagents, allylboronation, reduction, and thermal transformations are discussed.The chemistry of 2,3-dihydro-2,3-pyrrolediones condensed with azaheterocycles on the [a] side first evolved in the seventies, when the application of 2,3-dihydro-2,3-pyrroledione derivatives as synthetic blocks for the construction of alkaloid molecules was first demonstrated [1][2][3][4][5][6][7].It should be mentioned that up to the beginning of the nineties these annelated dihydropyrrolediones were studied almost exclusively as subjects for photoreduction and photocyclization or as dienophiles in DielsAlder reactions (for the production of intermediate compounds in the synthesis of alkaloids). A large part of these papers belong to certain groups of investigators [1][2][3][4][5].…”

“…The chemistry of 2,3-dihydro-2,3-pyrrolediones condensed with azaheterocycles on the [a] side first evolved in the seventies, when the application of 2,3-dihydro-2,3-pyrroledione derivatives as synthetic blocks for the construction of alkaloid molecules was first demonstrated [1][2][3][4][5][6][7].…”

“…The review does not include data on the chemistry of isatins and their aza analogs, which were described in [8], or data on the cycloaddition of these pyrrolediones, which have been discussed before [1][2][3][4][5][6][7][9][10][11] and were reviewed in [11].…”

“…The reaction is usually conducted in an inert aprotic solvent (ether [7,[9][10][11], chloroform [9,12], dichloromethane [13], 1,2-dimethoxyethane [14], benzene [15,16], dioxane [17]) or in pyridine in the range of 0-100°C for 1.5-3.5 h. The yields of the desired products are as a rule good particularly if the enamine contains at least one electron-withdrawing substituent (a COR or COOR group); there has been are no mention of the isolation of side products.…”