Asymmetric total syntheses of ecteinascidin 597 and ecteinascidin 583
2006
Abstract
The limited availability of bioactive natural products for pharmaceutical studies and drug development is a problem that can be solved, in principle, by total synthesis. The potent antitumor marine natural products ecteinascidin 597 (I; R = Me) and ecteinascidin 583 (I; R = H) have now been synthesized from readily accessible starting materials in a highly convergent and stereoselective fashion (see scheme). [on SciFinder (R)]
Details
Title
Asymmetric total syntheses of ecteinascidin 597 and ecteinascidin 583
Author(s)
Chen, Jinchun ; Chen, Xiaochuan ; Willot, Matthieu ; Zhu, Jieping
Published in
Angewandte Chemie, International Edition
Volume
45
Issue
47
Pages
8028-8032
Date
2006
ISSN
1433-7851
Keywords
Absolute configuration; Stereoselective synthesis (asym. total syntheses of ecteinascidins 597 and 583); Synthons (chiral; asym. total syntheses of ecteinascidins 597 and 583); Alkaloids Role: SPN (Synthetic preparation); PREP (Preparation) (marine; asym. total syntheses of ecteinascidins 597 and 583); asym synthesis alkaloid ecteinascidin 597 583
Note
CAN 146:252015
31-6
Alkaloids
Institut de Chimie des Substances Naturelles,Gif-sur-Yvette Cedex,Fr.
Journal
written in English.
686776-27-2 ((S)-[3-Hydroxy-4-methoxy-5-methylphenyl]alanol) Role: RCT (Reactant), RACT (Reactant or reagent) (Pictet-Spengler reaction of, with (S)-Garner aldehyde; asym. total syntheses of ecteinascidins 597 and 583); 102308-32-7 ((S)-Garner aldehyde) Role: RCT (Reactant), RACT (Reactant or reagent) (Pictet-Spengler reaction of, with (S)-[3-methoxy-4-methoxy-5-methylphenyl]alanol; asym. total syntheses of ecteinascidins 597 and 583); 17341-93-4 Role: RCT (Reactant), RACT (Reactant or reagent) (asym. total syntheses of ecteinascidins 597 and 583); 184300-07-0P (Ecteinascidin 597); 184300-08-1P (Ecteinascidin 583) Role: SPN (Synthetic preparation), PREP (Preparation) (asym. total syntheses of ecteinascidins 597 and 583); 925451-83-8 Role: RCT (Reactant), RACT (Reactant or reagent) (attempted condensation of, with benzyloxyacetaldehyde and glyoxylate; asym. total syntheses of ecteinascidins 597 and 583); 924-44-7 (Ethyl glyoxylate); 60656-87-3 (2-(Benzyloxy)acetaldehyde) Role: RCT (Reactant), RACT (Reactant or reagent) (attempted condensation of, with isoquinolinylamine piperonyl deriv.; asym. total syntheses of ecteinascidins 597 and 583); 854022-02-9 (N-[2,2,2-Trichloroethoxycarbonyl]-S-(trimethoxytrityl)-L-cysteine) Role: RCT (Reactant), RACT (Reactant or reagent) (esterification of, with bisisoquinoline deriv.; asym. total syntheses of ecteinascidins 597 and 583); 107-21-1 (Ethylene glycol) Role: RCT (Reactant), RACT (Reactant or reagent) (monoprotection of, with Troc-Cl; asym. total syntheses of ecteinascidins 597 and 583); 69404-94-0P (Vanillin tert-butyldimethylsilyl ether) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Baeyer-Villiger oxidn. of; asym. total syntheses of ecteinascidins 597 and 583); 925451-98-5P (2-[(2,2,2-Trichloroethoxycarbonyl)oxy]ethanol) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Dess-Martin oxidn. of; asym. total syntheses of ecteinascidins 597 and 583); 925451-70-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Grignard reaction of, with methoxybenzenediol Grignard deriv.; asym. total syntheses of ecteinascidins 597 and 583); 874758-58-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and N-/O-deisopropylidenation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-89-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and N-deprotection of; asym. total syntheses of ecteinascidins 597 and 583); 925451-88-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and N-methylation or N-deprotection of; asym. total syntheses of ecteinascidins 597 and 583); 925451-95-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-allylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-73-6P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-dealkylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-87-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-deallylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-79-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-deallylation, or Swern oxidn./cyclization and cyanation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-80-5P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-deethoxycarbonylation, or O-deallylation/N-deallyloxycarbonylation of; asym. total syntheses of ecteinascidins 597 and 583); 402469-27-6P; 925451-76-9P Role: RC (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-methoxymethylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-77-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Pictet-Spengler reaction of, with O-Troc-glycoaldehyde; asym. total syntheses of ecteinascidins 597 and 583); 925451-78-1P (O-(2,2,2-Trichloroethoxycarbonyl)glycoaldehyde) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Pictet-Spengler reaction of, with isoquinolinylmethanamine alpha -benzyl deriv.; asym. total syntheses of ecteinascidins 597 and 583); 925451-85-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and S-deprotection of; asym. total syntheses of ecteinascidins 597 and 583); 925451-75-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Swern. oxidn. of; asym. total syntheses of ecteinascidins 597 and 583); 925451-81-6P; 925451-82-7P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and abs. configuration of; asym. total syntheses of ecteinascidins 597 and 583); 874758-72-2P; 925451-93-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and acetylation of; asym. total syntheses of ecteinascidins 597 and 583); 874758-56-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and acylation of, with allyloxycarbonyl chloride; asym. total syntheses of ecteinascidins 597 and 583); 874758-71-1P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and allylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-90-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and attempted intramol. cyclization/sulfuration of; asym. total syntheses of ecteinascidins 597 and 583); 925451-92-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and deacetylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-84-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and esterification by, of L-cysteine deriv.; asym. total syntheses of ecteinascidins 597 and 583); 259220-89-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and ortho-methylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-96-3P; 925451-97-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and oxidative decyanation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-68-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., Grignard formation and aldol reaction of, with isoquinolinylglycinal deriv.; asym. total syntheses of ecteinascidins 597 and 583); 925451-91-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., N-deprotection and desilylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-86-1P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., O-demethoxymethyaltion and intramol. sulfuration/cyclization of; asym. total syntheses of ecteinascidins 597 and 583); 121-33-5 (Vanillin) Role: RCT (Reactant), RACT (Reactant or reagent) (silylation of; asym. total syntheses of ecteinascidins 597 and 583)
31-6
Alkaloids
Institut de Chimie des Substances Naturelles,Gif-sur-Yvette Cedex,Fr.
Journal
written in English.
686776-27-2 ((S)-[3-Hydroxy-4-methoxy-5-methylphenyl]alanol) Role: RCT (Reactant), RACT (Reactant or reagent) (Pictet-Spengler reaction of, with (S)-Garner aldehyde; asym. total syntheses of ecteinascidins 597 and 583); 102308-32-7 ((S)-Garner aldehyde) Role: RCT (Reactant), RACT (Reactant or reagent) (Pictet-Spengler reaction of, with (S)-[3-methoxy-4-methoxy-5-methylphenyl]alanol; asym. total syntheses of ecteinascidins 597 and 583); 17341-93-4 Role: RCT (Reactant), RACT (Reactant or reagent) (asym. total syntheses of ecteinascidins 597 and 583); 184300-07-0P (Ecteinascidin 597); 184300-08-1P (Ecteinascidin 583) Role: SPN (Synthetic preparation), PREP (Preparation) (asym. total syntheses of ecteinascidins 597 and 583); 925451-83-8 Role: RCT (Reactant), RACT (Reactant or reagent) (attempted condensation of, with benzyloxyacetaldehyde and glyoxylate; asym. total syntheses of ecteinascidins 597 and 583); 924-44-7 (Ethyl glyoxylate); 60656-87-3 (2-(Benzyloxy)acetaldehyde) Role: RCT (Reactant), RACT (Reactant or reagent) (attempted condensation of, with isoquinolinylamine piperonyl deriv.; asym. total syntheses of ecteinascidins 597 and 583); 854022-02-9 (N-[2,2,2-Trichloroethoxycarbonyl]-S-(trimethoxytrityl)-L-cysteine) Role: RCT (Reactant), RACT (Reactant or reagent) (esterification of, with bisisoquinoline deriv.; asym. total syntheses of ecteinascidins 597 and 583); 107-21-1 (Ethylene glycol) Role: RCT (Reactant), RACT (Reactant or reagent) (monoprotection of, with Troc-Cl; asym. total syntheses of ecteinascidins 597 and 583); 69404-94-0P (Vanillin tert-butyldimethylsilyl ether) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Baeyer-Villiger oxidn. of; asym. total syntheses of ecteinascidins 597 and 583); 925451-98-5P (2-[(2,2,2-Trichloroethoxycarbonyl)oxy]ethanol) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Dess-Martin oxidn. of; asym. total syntheses of ecteinascidins 597 and 583); 925451-70-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Grignard reaction of, with methoxybenzenediol Grignard deriv.; asym. total syntheses of ecteinascidins 597 and 583); 874758-58-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and N-/O-deisopropylidenation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-89-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and N-deprotection of; asym. total syntheses of ecteinascidins 597 and 583); 925451-88-3P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and N-methylation or N-deprotection of; asym. total syntheses of ecteinascidins 597 and 583); 925451-95-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-allylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-73-6P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-dealkylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-87-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-deallylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-79-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-deallylation, or Swern oxidn./cyclization and cyanation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-80-5P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-deethoxycarbonylation, or O-deallylation/N-deallyloxycarbonylation of; asym. total syntheses of ecteinascidins 597 and 583); 402469-27-6P; 925451-76-9P Role: RC (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and O-methoxymethylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-77-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Pictet-Spengler reaction of, with O-Troc-glycoaldehyde; asym. total syntheses of ecteinascidins 597 and 583); 925451-78-1P (O-(2,2,2-Trichloroethoxycarbonyl)glycoaldehyde) Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Pictet-Spengler reaction of, with isoquinolinylmethanamine alpha -benzyl deriv.; asym. total syntheses of ecteinascidins 597 and 583); 925451-85-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and S-deprotection of; asym. total syntheses of ecteinascidins 597 and 583); 925451-75-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and Swern. oxidn. of; asym. total syntheses of ecteinascidins 597 and 583); 925451-81-6P; 925451-82-7P Role: PRP (Properties), SPN (Synthetic preparation), PREP (Preparation) (prepn. and abs. configuration of; asym. total syntheses of ecteinascidins 597 and 583); 874758-72-2P; 925451-93-0P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and acetylation of; asym. total syntheses of ecteinascidins 597 and 583); 874758-56-2P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and acylation of, with allyloxycarbonyl chloride; asym. total syntheses of ecteinascidins 597 and 583); 874758-71-1P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and allylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-90-7P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and attempted intramol. cyclization/sulfuration of; asym. total syntheses of ecteinascidins 597 and 583); 925451-92-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and deacetylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-84-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and esterification by, of L-cysteine deriv.; asym. total syntheses of ecteinascidins 597 and 583); 259220-89-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and ortho-methylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-96-3P; 925451-97-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. and oxidative decyanation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-68-9P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., Grignard formation and aldol reaction of, with isoquinolinylglycinal deriv.; asym. total syntheses of ecteinascidins 597 and 583); 925451-91-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., N-deprotection and desilylation of; asym. total syntheses of ecteinascidins 597 and 583); 925451-86-1P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn., O-demethoxymethyaltion and intramol. sulfuration/cyclization of; asym. total syntheses of ecteinascidins 597 and 583); 121-33-5 (Vanillin) Role: RCT (Reactant), RACT (Reactant or reagent) (silylation of; asym. total syntheses of ecteinascidins 597 and 583)
Laboratories
LSPN
Record Appears in
Scientific production and competences > SB - School of Basic Sciences > ISIC - Institute of Chemical Sciences and Engineering > LSPN - Laboratory of synthesis and natural products
Peer-reviewed publications
Work outside EPFL
Journal Articles
Published
Peer-reviewed publications
Work outside EPFL
Journal Articles
Published
Record creation date
2010-11-25