Total synthesis of the natural carbazoles Murrayanine and Murrayafoline A, based on the regioselective Diels-Alder addition of exo-2-oxazolidinone dienes

Adriana Benavides, Javier Peralta, Francisco Delgado, Joaquín Tamariz

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

A new synthesis of the natural carbazoles Murrayanine (1) and Murrayafoline A (3) is described. The key step in the synthetic route involved the regioselective cycloaddition of the diene 4,5-dimethylene-3-phenyl-1,3- oxazolidin-2-one (4) to acrolein (6) catalyzed by Lewis acids at low temperature. Direct aromatization of the substituted cyclohexene moiety of adduct 7, and further hydrolysis of the 2-oxazolidinone ring, proved to be a more efficient strategy than the opposite synthetic sequence for the preparation of the corresponding arylphenylamines 14 and 18. Palladium-promoted cyclization of the latter furnished the desired carbazoles 1 and 3 in high overall yields.
Original languageAmerican English
Pages (from-to)2499-2504
Number of pages2248
JournalSynthesis
DOIs
StatePublished - 18 Oct 2004

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Carbazoles
Oxazolidinones
Aromatization
Cycloaddition
Cyclization
Palladium
Hydrolysis
Acrolein
Lewis Acids
Acids
Cycloaddition Reaction
Temperature
murrayafoline A
murrayanine

Cite this

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title = "Total synthesis of the natural carbazoles Murrayanine and Murrayafoline A, based on the regioselective Diels-Alder addition of exo-2-oxazolidinone dienes",
abstract = "A new synthesis of the natural carbazoles Murrayanine (1) and Murrayafoline A (3) is described. The key step in the synthetic route involved the regioselective cycloaddition of the diene 4,5-dimethylene-3-phenyl-1,3- oxazolidin-2-one (4) to acrolein (6) catalyzed by Lewis acids at low temperature. Direct aromatization of the substituted cyclohexene moiety of adduct 7, and further hydrolysis of the 2-oxazolidinone ring, proved to be a more efficient strategy than the opposite synthetic sequence for the preparation of the corresponding arylphenylamines 14 and 18. Palladium-promoted cyclization of the latter furnished the desired carbazoles 1 and 3 in high overall yields.",
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T1 - Total synthesis of the natural carbazoles Murrayanine and Murrayafoline A, based on the regioselective Diels-Alder addition of exo-2-oxazolidinone dienes

AU - Benavides, Adriana

AU - Peralta, Javier

AU - Delgado, Francisco

AU - Tamariz, Joaquín

PY - 2004/10/18

Y1 - 2004/10/18

N2 - A new synthesis of the natural carbazoles Murrayanine (1) and Murrayafoline A (3) is described. The key step in the synthetic route involved the regioselective cycloaddition of the diene 4,5-dimethylene-3-phenyl-1,3- oxazolidin-2-one (4) to acrolein (6) catalyzed by Lewis acids at low temperature. Direct aromatization of the substituted cyclohexene moiety of adduct 7, and further hydrolysis of the 2-oxazolidinone ring, proved to be a more efficient strategy than the opposite synthetic sequence for the preparation of the corresponding arylphenylamines 14 and 18. Palladium-promoted cyclization of the latter furnished the desired carbazoles 1 and 3 in high overall yields.

AB - A new synthesis of the natural carbazoles Murrayanine (1) and Murrayafoline A (3) is described. The key step in the synthetic route involved the regioselective cycloaddition of the diene 4,5-dimethylene-3-phenyl-1,3- oxazolidin-2-one (4) to acrolein (6) catalyzed by Lewis acids at low temperature. Direct aromatization of the substituted cyclohexene moiety of adduct 7, and further hydrolysis of the 2-oxazolidinone ring, proved to be a more efficient strategy than the opposite synthetic sequence for the preparation of the corresponding arylphenylamines 14 and 18. Palladium-promoted cyclization of the latter furnished the desired carbazoles 1 and 3 in high overall yields.

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