The Total Synthesis of (±)‐Fortucine and a Revision of the Structure of Kirkine

Biechy, Aurélien; Hachisu, Shuji; Quiclet‐Sire, Béatrice; Ricard, Louis; Zard, Samir Z.

doi:10.1002/anie.200704996

Cited by 55 publications

(19 citation statements)

References 12 publications

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“…The total synthesis of fortucine ( 15 ), also hinges on the sequential fashioning of an indolizidine-type skeleton, with the second cyclisation taking place on an aromatic ring (Scheme 3) [14–15]. The formation of the amidyl radical in this case calls for a different precursor and does not involve a stannane reagent.…”

Section: Reviewmentioning

confidence: 99%

Some aspects of radical chemistry in the assembly of complex molecular architectures

Quiclet‐Sire¹,

Zard²

2013

Beilstein J. Org. Chem.

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SummaryThis review article describes briefly some of the radical processes developed in the authors’ laboratory as they pertain to the concise assembly of complex molecular scaffolds. The emphasis is placed on the use of nitrogen-centred radicals, on the degenerate addition–transfer of xanthates, especially on its potential for intermolecular carbon–carbon bond formation, and on the generation and capture of radicals through electron transfer processes.

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Section: Reviewmentioning

confidence: 99%

Some aspects of radical chemistry in the assembly of complex molecular architectures

Quiclet‐Sire¹,

Zard²

2013

Beilstein J. Org. Chem.

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“…A racemic synthesis of fortucine was reported by Zard and coworkers (Biechy et al, 2008 , 2009 ) and involved a noteworthy radical cascade reaction for formation of the main core of the target. We envisaged an enantioselective synthesis of fortucine based on the retrosynthesis presented in Figure 12 .…”

Section: Syntheses Ok Alkaloids Bearing a Cyclic Trisubstituted Alkenmentioning

confidence: 99%

Total synthesis of natural products using hypervalent iodine reagents

2015

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We present a review of natural product syntheses accomplished in our laboratory during the last 5 years. Each synthetic route features a phenol dearomatization promoted by an environmentally benign hypervalent iodine reagent. The dearomatizations demonstrate the “aromatic ring umpolung” concept, and involve stereoselective remodeling of the inert unsaturations of a phenol into a highly functionalized key intermediate that may contain a quaternary carbon center and a prochiral dienone system. Several new oxidative strategies were employed, including transpositions (1,3-alkyl shift and Prins-pinacol), a polycyclization, an ipso rearrangement, and direct nucleophilic additions at the phenol para position. Several alkaloids, heterocyclic compounds, and a polycyclic core have been achieved, including sceletenone (a serotonin reuptake inhibitor), acetylaspidoalbidine (an antitumor agent), fortucine (antiviral and antitumor), erysotramidine (curare-like effect), platensimycin (an antibiotic), and the main core of a kaurane diterpene (immunosuppressive agent and stimulator of apoptosis). These concise and in some cases enantioselective syntheses effectively demonstrate the importance of hypervalent iodine reagents in the total synthesis of bioactive natural products.

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“…1 Polycyclic molecules bearing tertiary amines are of special interest because they possess the rigid structural framework, high density of sp 3 centers, and low molecular weight profile associated with “drug-like” molecules. 2 We were attracted to the potential utility of neutral aminyl radicals to construct these frameworks because radical cascades have well established reactivity with predictable bond construction outcomes.…”

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Synthetic and Computational Study of Tin-Free Reductive Tandem Cyclizations of Neutral Aminyl Radicals

et al. 2018

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5-exo, 5-exo Cyclizations of conformationally unbiased propargylic aminyl radicals proceed with excellent yield, chemoselectiv ity, and diastereoselectivity under tin-free reductive cyclization conditions, regardless of the electronic environments and intermediate radical stabilization resulting from various olefin substituents. These conditions avoid the need for slow addition of initiator and reductant. By contrast, analogous 6-exo, 5-exo cyclizations require substituents capable of intermediate radical stabilization to avoid premature reduction products. These experimental results are corroborated by computations that further establish the reactivity of these aminyl radicals upon exposure to tin-free cyclization conditions.

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The Total Synthesis of (±)‐Fortucine and a Revision of the Structure of Kirkine

Abstract: communicationInternational audienc

Cited by 55 publications

References 12 publications

Some aspects of radical chemistry in the assembly of complex molecular architectures

Some aspects of radical chemistry in the assembly of complex molecular architectures

Total synthesis of natural products using hypervalent iodine reagents

Synthetic and Computational Study of Tin-Free Reductive Tandem Cyclizations of Neutral Aminyl Radicals

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