Total synthesis of (S)-(−)-cyclooroidin

Patel, Jignesh J.; Pelloux-Léon, Nadia; Minassian, Frédéric; Vallée, Yannick

doi:10.1016/j.tetlet.2006.05.130

Cited by 34 publications

(22 citation statements)

References 18 publications

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“…65 HOBT = N -hydroxybenzotriazole, DCC = dicyclohexylcarbodiimide, DMF = N-N -dimethylformamide, THF = tetrahydrofuran, NBS = N -bromosuccinimide. IBX = Iodoxybenzoic acid, TFA = trifluoroacetic acid…”

Section: Figmentioning

confidence: 99%

Biosynthesis, asymmetric synthesis, and pharmacology, including cellular targets, of the pyrrole-2-aminoimidazole marine alkaloids

et al. 2011

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The pyrrole-2-aminoimidazole (P-2-AI) alkaloids are a growing family of marine alkaloids, now numbering well over 150 members, with high topographical and biological information content. Their intriguing structural complexity, rich and compact stereochemical content, high N to C ratio (~1:2), and increasingly studied biological activities are attracting a growing number of researchers from numerous disciplines world-wide. This review surveys advances in this area with a focus on the structural diversity, biosynthetic hypotheses with increasing but still rare verifying experimental studies, asymmetric syntheses, and biological studies including cellular target receptor isolation studies of this stimulating and exciting alkaloid family.

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Section: Figmentioning

confidence: 99%

Biosynthesis, asymmetric synthesis, and pharmacology, including cellular targets, of the pyrrole-2-aminoimidazole marine alkaloids

et al. 2011

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“…The use of chiral pools and the resolution of racemates are the only synthetic routes to 1 and 2 to date. [3][4][5] During our ongoing research addressing the functionalization of polycyclic indoles, [6] we recently communicated an efficient Pd-catalyzed approach to tetrahydro-b-carbolines through regio-and enantioselective C3-allylic nucleophilic alkylation (up to 97 % ee).[7] Unfortunately, all our attempts to exploit such an approach to perform enantioselective indolyl-N1 ring-closing reactions were unsuccessful. Herein, we describe the first highly enantioselective synthesis of molecular motifs of type 1 through a phase-transfer-catalyzed [8] aza-Michael addition.…”

mentioning

confidence: 99%

Enantioselective Phase‐Transfer‐Catalyzed Intramolecular Aza‐Michael Reaction: Effective Route to Pyrazino‐Indole Compounds

et al. 2008

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The preparation of enantiomerically pure compounds has become a stringent requirement for pharmaceutical synthesis. [1] In this context, asymmetric catalysis is probably the most attractive procedure for the synthesis of active pharmaceutical ingredients (APIs) due to environmental, operational, and economic benefits.3,4-Dihydropyrazino[1,2-a]indol-1(2H)-ones 1 (see Scheme 1) have attracted much attention due to the broad scope of their biological activities (that is, their antifungal properties, noncompetitive antihistamine activity, and specific inhibition of serotonergic receptors).[2] Moreover, recent patents reported the effectiveness of the corresponding 1,2,3,4-tetrahydropyrazino[1,2-a]indoles 2 (Scheme 1) as antiobesity agents and in the treatment and prevention of noninsulin-dependent diabetes. [3] From these studies, the importance of the absolute configuration of the stereocenters on the pharmacological activity emerged clearly. Moreover, since the piperazine compounds 2 are readily obtainable from 1,[3] the development of an effective stereoselective synthetic route to pyrazino-indol-1-ones 1 would be extremely valuable. The use of chiral pools and the resolution of racemates are the only synthetic routes to 1 and 2 to date. [3][4][5] During our ongoing research addressing the functionalization of polycyclic indoles, [6] we recently communicated an efficient Pd-catalyzed approach to tetrahydro-b-carbolines through regio-and enantioselective C3-allylic nucleophilic alkylation (up to 97 % ee).[7] Unfortunately, all our attempts to exploit such an approach to perform enantioselective indolyl-N1 ring-closing reactions were unsuccessful. Herein, we describe the first highly enantioselective synthesis of molecular motifs of type 1 through a phase-transfer-catalyzed [8] aza-Michael addition.[9]The employment of a metal-free approach [10] stems from our recent findings on the intramolecular base-catalyzed synthesis of 1, from readily available precursors 3 (Scheme 2).[11] However, the use of Lewis acid catalysis in the present ring-closing reaction failed, probably due to the poor electrophilic character of the a,b-unsaturated ester and to low catalyst turnover as a result of starting material/ product inhibition (that is, a metallo-poisoning effect exerted by the strongly coordinating amide group). Searching for an enantioselective variant, we firstly turned our attention to chiral organic bases such as the Cinchona alkaloids and sparteine, which gave disappointing results in the cyclizations of 3 a (X = H; toluene, reflux, 48 h, 0 % ee). We reasoned that the unsatisfactory stereoinduction could be ascribable to the formation of flexible and not sufficiently tight ion pairs between the ammonium salt of the quinuclidine ring and the nucleophilic indolate intermediate (Figure 1 a).

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“…38,39,42 While attempts to synthesize ageliferins by inducing the dimerization of 1 via a thermal Diels–Alder reaction have not been successful, 14c the Romo group and the Lovely group successfully used the Diels–Alder reaction to construct the core skeleton of 9a . 19,20 The Ohta group also used this Diels–Alder approach to accomplish the synthesis of 12,12’-dimethylageliferin in 2002.…”

Section: Total Synthesesmentioning

confidence: 99%

“…For example, there are several reports of the synthesis of cyclooroidin ( 2 ), 14 agelastatins ( 3 ), 15 and dibromophakellin/dibromophakellstatin ( 4 ). 16 The most synthetically challenging family members are the cyclic dimers.…”

Section: Introductionmentioning

confidence: 99%

Dimeric pyrrole–imidazole alkaloids: synthetic approaches and biosynthetic hypotheses

Wang

et al. 2014

Chem. Commun.

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The pyrrole-imidazole alkaloids are a group of structurally unique and biologically interesting marine sponge metabolites. Among them, the cyclic dimers have caught synthetic chemists’ attention particularly. Numerous synthetic strategies have been developed and various biosynthetic hypotheses have been proposed for these fascinating natural products. We discuss herein the synthetic approaches and the biosynthetic insights obtained from these studies.

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Total synthesis of (S)-(−)-cyclooroidin

Cited by 34 publications

References 18 publications

Biosynthesis, asymmetric synthesis, and pharmacology, including cellular targets, of the pyrrole-2-aminoimidazole marine alkaloids

Biosynthesis, asymmetric synthesis, and pharmacology, including cellular targets, of the pyrrole-2-aminoimidazole marine alkaloids

Enantioselective Phase‐Transfer‐Catalyzed Intramolecular Aza‐Michael Reaction: Effective Route to Pyrazino‐Indole Compounds

Dimeric pyrrole–imidazole alkaloids: synthetic approaches and biosynthetic hypotheses

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