AgNTf2-Mediated Arylation of Bromopyrroloindolines

Soichiro, Sato; Hirayama, Azusa; Tohma, Adachi; Kawauchi, Daichi; Ueda, Hirofumi; Tokuyama, Hidetoshi

doi:10.3987/com-17-13777

Cited by 4 publications

(3 citation statements)

References 66 publications

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“…With this synthetic background, our group undertook synthetic studies of haplophytine, which seems to be one of the most synthetically difficult dimeric indole alkaloids. Herein, I report the first total synthesis of haplophytine 22) via a silver salt-mediated coupling reaction between two indole units and its second-generation synthesis 23) through a convergent synthetic route. Furthermore, we applied the silver bis(trifluoromethanesulfonyl) imide (AgNTf 2 )-mediated coupling reaction discovered in the synthesis of haplophytine to the introduction of aryl moiety into pyrroloindoline 24) and total syntheses of T988s.…”

Section: Reviewmentioning

confidence: 99%

“…The bromopyrroloindoline 76 could be readily prepared from D-tryptophan (78) and D-serine (79) according to the procedure reported by Sodeoka and colleagues. 79,80) Initially, this project started from the investigation of the AgNTf 2 -mediated nucleophilic substitution reaction of entbromopyrroloindoline 76, which can easily be prepared from natural amino acids. After diastereoselective bromocyclization of ent-77 according to Sodeoka's procedure, we examined the nucleophilic substitution reaction of ent-76 with various silver salts ( Fig.…”

Section: Total Synthesis Of T988smentioning

confidence: 99%

“…After sequential protection of the resulting primary alcohol and indole NH, 91 was converted to dioxopiperazine 82 via removal of the Cbz group followed by base treatment. Since bromocyclization of 82 using NBS in MeCN according to Sodeoka's procedure 79,80) gave an approx. 1 : 1 mixture of the desired bromopyrroloindoline 81 and its diastereomer ( Fig.…”

Section: Total Synthesis Of T988smentioning

confidence: 99%

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Synthetic Studies toward Dimeric Indole Alkaloids Based on Convergent Synthetic Strategy

Ueda

2020

CHEMICAL & PHARMACEUTICAL BULLETIN

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The total syntheses of dimeric indole alkaloids, haplophytine, and T988s are described. These dimeric compounds comprising two structurally different indole units are ubiquitous in nature, and many possess pharmaceutically important activities. To realize an efficient chemical synthesis of these dimeric indole alkaloids, the establishment of convergent synthetic strategies and development of new coupling methods are indispensable. The linkage of two highly functionalized units at a late stage of the synthesis frequently induces synthetic problems such as chemoselectivity and steric repulsion. Moreover, although transition metal-catalyzed reactions are usually an effective method for the cross-coupling of two units, the application of these cross-coupling reactions to bond formation involving a sterically hindered C(sp 3) is often difficult. Thus, even with precise modern synthetic methods, it is currently difficult to realize convergent syntheses of dimeric indole alkaloids possessing a quaternary carbon linking two units. To combat these synthetic problems, we developed a synthetic method to link two indole units using an Ag-mediated nucleophilic substitution reaction. In this review, we provide a detailed discussion of convergent synthetic strategies and coupling methods for dimeric indole alkaloids.

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Section: Reviewmentioning

confidence: 99%

Section: Total Synthesis Of T988smentioning

confidence: 99%

Section: Total Synthesis Of T988smentioning

confidence: 99%

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Synthetic Studies toward Dimeric Indole Alkaloids Based on Convergent Synthetic Strategy

Ueda

2020

CHEMICAL & PHARMACEUTICAL BULLETIN

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AgNTf₂-Mediated Allylation with Allylsilanes at C3a-Position of Hexahydropyrroloindoles: Application to Total Syntheses of Amauromine Alkaloids

et al. 2017

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A protocol for the allylation at the C3a-position of hexahydropyrroloindole using allylsilanes is developed. AgNTf proved to be an efficient activator of halopyrroloindoline substrates. This method is applicable to the introduction of various allyl groups including the reverse prenyl group. The utility of this reaction is demonstrated by total synthesis of amauromine alkaloids. Stepwise bromocyclizations of the bis-indolylmethyl diketopiperazine derivative and subsequent double reverse prenylation furnished (+)-novoamauromine and (-)-epiamauromine.

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Construction of Indole Structure on Pyrroloindolines via AgNTf₂-Mediated Amination/Cyclization Cascade: Application to Total Synthesis of (+)-Pestalazine B

2019

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An N-linked indole structure was constructed on the 3a-position of pyrroloindoline derivatives via a cascade process involving silver-mediated amination of bromopyrroloindolines with 2-ethynylanilines with subsequent 5-endo-dig cyclization. In this reaction, AgNTf2 was used as a tandem reagent, which activated the bromo group as a σ-Lewis acid and the alkyne moiety as a π-Lewis acid. Switching from the initial step to the second step was conducted by controlling the temperature. This protocol was applied to the synthesis of various pyrroloindolines, α-carboline, and furoindolines and the total synthesis of a dimeric indole alkaloid, (+)-pestalazine B.

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AgNTf2-Mediated Arylation of Bromopyrroloindolines

Cited by 4 publications

References 66 publications

Synthetic Studies toward Dimeric Indole Alkaloids Based on Convergent Synthetic Strategy

Synthetic Studies toward Dimeric Indole Alkaloids Based on Convergent Synthetic Strategy

AgNTf₂-Mediated Allylation with Allylsilanes at C3a-Position of Hexahydropyrroloindoles: Application to Total Syntheses of Amauromine Alkaloids

Construction of Indole Structure on Pyrroloindolines via AgNTf₂-Mediated Amination/Cyclization Cascade: Application to Total Synthesis of (+)-Pestalazine B

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AgNTf2-Mediated Arylation of Bromopyrroloindolines

Cited by 4 publications

References 66 publications

Synthetic Studies toward Dimeric Indole Alkaloids Based on Convergent Synthetic Strategy

Synthetic Studies toward Dimeric Indole Alkaloids Based on Convergent Synthetic Strategy

AgNTf2-Mediated Allylation with Allylsilanes at C3a-Position of Hexahydropyrroloindoles: Application to Total Syntheses of Amauromine Alkaloids

Construction of Indole Structure on Pyrroloindolines via AgNTf2-Mediated Amination/Cyclization Cascade: Application to Total Synthesis of (+)-Pestalazine B

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AgNTf₂-Mediated Allylation with Allylsilanes at C3a-Position of Hexahydropyrroloindoles: Application to Total Syntheses of Amauromine Alkaloids

Construction of Indole Structure on Pyrroloindolines via AgNTf₂-Mediated Amination/Cyclization Cascade: Application to Total Synthesis of (+)-Pestalazine B