Total Synthesis of Amphidinolide J

Barbazanges, Marion; Meyer, Christophe; Cossy, Janine

doi:10.1021/ol801708x

Cited by 42 publications

(13 citation statements)

References 29 publications

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“…52 In addition to the case studies discussed above, many other instructive applications of the '9-methoxy-9-BBN variant' to the late-stage assembly of complex bioactive target molecules were reported in the literature (Table 2). This includes, inter alia, elegant partial or total syntheses of amphidinolide E, 53 amphidinolide J, 54 kendomycin, 55,56 iridal, 57 the haterumalides, 58 (putative) iriomoteolide-1a, 59-61 neopeltolide, 62 cordiaquinone K, 63 plakortone B, 64 and didemnaketal B. 46,65 Collectively, these examples illustrate the outstanding performance and functional group tolerance of the '9-MeO-9-BBN variant' of the Suzuki reaction, which is a mature and enabling methodology for natural product total synthesis.…”

Section: Mycolactonementioning

confidence: 99%

Suzuki reactions of extended scope: the ‘9-MeO-9-BBN variant’ as a complementary format for cross-coupling

Seidel

Fürstner

2012

Chem. Commun.

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While the Suzuki coupling has gained paramount importance, the basic set-up of the reaction has remained essentially unchanged for decades. It consists of the palladium-catalyzed coupling of organoboron reagents with aryl- or alkenyl halides, -sulfonates or related electrophiles in the presence of a base. One of the few alternative formats for this transformation is the '9-MeO-9-BBN variant', which is distinguished by not requiring an added base as a promoter. Rather, polar organometallic reagents R-M (R = Me, alkyl, aryl, heteroaryl, alkenyl, alkynyl etc.) are first intercepted with 9-MeO-9-BBN to give the corresponding borinate complexes, which then pass the R-group onto an organopalladium complex generated in situ as the electrophilic partner. This procedure allowed the structural reach of the Suzuki coupling to be extended, and served in a host of advanced applications, most notably for elaborate sp-sp(2) and sp(3)-sp(2) coupling processes.

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Section: Mycolactonementioning

confidence: 99%

Suzuki reactions of extended scope: the ‘9-MeO-9-BBN variant’ as a complementary format for cross-coupling

Seidel

Fürstner

2012

Chem. Commun.

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“…Moreover, disubstitution at C3, which hampered the thermal [2,3]-sigmatropic shift of cyclopropenylcarbinyl phosphonites, is well accommodated by the Ireland–Claisen rearrangement. It was observed that the rearrangement of 3a , although favored by the relief of ring strain, did not experience significant rate acceleration compared to regular allylic glycolates. , For a more meaningful comparison, the Ireland–Claisen rearrangement of glycolate 3b substituted by a styryl group was studied. After hydrolysis and esterification, analysis of the crude product by 1 H NMR spectroscopy indicated the exclusive formation of vinylcyclopropene 8 , which was isolated in 60% yield.…”

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confidence: 99%

Synthesis of Functionalized Alkylidenecyclopropanes by Ireland–Claisen Rearrangement of Cyclopropenylcarbinyl Esters

Ernouf

Brayer²,

Folléas³

et al. 2015

Org. Lett.

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Glycolates or glycinates derived from diversely substituted secondary cyclopropenylcarbinols have been involved for the first time in an Ireland-Claisen rearrangement. This reaction allows an efficient and stereoselective access to highly functionalized alkylidenecyclopropanes possessing an α-hydroxy or α-amino acid subunit, which in turn are valuable precursors of substituted cyclopropanes by diastereoselective hydrogenation of the exocyclic alkene.

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“…The transformation of 3 to ( R )-hydroxyaldehyde 6 was achieved in 4 steps. After converting acetal 3 into ketone 4 by the addition of propynylmagnesium bromide (THF, −78 to 0 °C, 94%), the ketone was enantioselectively reduced by applying a Noyori asymmetric hydrogen transfer using Ts‑DPEN-RuCl( p -cymene) I (10 mol %, i PrOH–CH 2 Cl 2 ) to produce 5 in 66% yield with an excellent ee (ee = 90%) . The reaction needed a high loading in Noyori’s catalyst (10 mol %) to increase the reaction rate, while at a lower loading (5 mol %) a competitive reduction of the triple bond was eroding the yields in the desired propargylic alcohol 5 .…”

Section: Results and Discussionmentioning

confidence: 99%

Intramolecular Diels–Alder Approaches to the Decalin Core of Verongidolide: The Origin of the exo-Selectivity, a DFT Analysis

et al. 2018

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Verongidolide is a natural macrolactone recently isolated from a New Caledonia sponge, Verongidolae. The structure of this natural product is similar to the structure of superstolides, also isolated from a New Caledonian sponge, Neosiphonia superstes. From a biological point of view, verongidolide and superstolides A and B present potent cytotoxicity against human oral carcinoma KB (0.3 nM). By comparing the H NMR chemical shifts as well as the coupling constants, we conclude that verongidolide possesses a cis-decalin core and we hypothesize that the relative configuration of the cis-decalin core is similar to the one of superstolide A. To verify this hypothesis, intramolecular and transannular Diels-Alder reactions were attempted to construct the decalin core. Unexpectedly, the selectivity of the Diels-Alder reactions was exo and an in-depth DFT calculation of the key reaction mechanism was achieved in order to understand the factors controlling this unexpected selectivity.

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Total Synthesis of Amphidinolide J

Cited by 42 publications

References 29 publications

Suzuki reactions of extended scope: the ‘9-MeO-9-BBN variant’ as a complementary format for cross-coupling

Suzuki reactions of extended scope: the ‘9-MeO-9-BBN variant’ as a complementary format for cross-coupling

Synthesis of Functionalized Alkylidenecyclopropanes by Ireland–Claisen Rearrangement of Cyclopropenylcarbinyl Esters

Intramolecular Diels–Alder Approaches to the Decalin Core of Verongidolide: The Origin of the exo-Selectivity, a DFT Analysis

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