Studies on the Synthesis of Tedanolide. 2. Stereoselective Synthesis of a Protected C(1)−C(12) Fragment

Roush, William; Newcom, Jason S.

doi:10.1021/ol0272343

Cited by 32 publications

(11 citation statements)

References 36 publications

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“…The allyloxycarbonyl group was also used but led to substantial elimination products upon subsequent transformation. Finally, the triethylsilyl group (TES) was chosen as a protecting group at this position 9x. Once the allylic hydroxyl group was converted into its TES ether, the p ‐methoxybenzyl (PMB) group on the primary hydroxyl group was transferred to the secondary alcohol by using the sequence of 2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone (DDQ) oxidation followed by reductive cleavage of the intermediate p ‐methoxyphenyl (PMP) acetal (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

The Synthesis of Desepoxy‐Isotedanolide – A Potential Biosynthetic Precursor of Tedanolide

2015

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The tedanolides are biologically active polyketides that exhibit a characteristic feature of an 18‐membered macrolactone generated from a primary hydroxyl group. In the realm of polyketides only secondary alcohols are generated by polyketidal transformations. With this knowledge, Taylor hypothesized that the observed macrolactone might arise from an intramolecular transesterification. To investigate this hypothetical transesterification, we completed the synthesis of desepoxy‐isotedanolide as tedanolide's putative biosynthetic precursor. This synthesis required a modified protecting group strategy, which proved to be non‐trivial. Unfortunately, it was not possible to accomplish the envisioned transesterification under laboratory conditions.

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Section: Resultsmentioning

confidence: 99%

The Synthesis of Desepoxy‐Isotedanolide – A Potential Biosynthetic Precursor of Tedanolide

2015

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“…Confirmation that the macrocyclization event occurred at the C(29) hydroxyl was deduced via a series of careful 1 H, 13 C, 13 C distortionless enhancement by polarization transfer, and heteronuclear multiple quantum correlation experiments. Completion of the synthesis of (ϩ)-13-deoxytedanolide (2) would now require differentiation of the C(15) and C(17) hydroxyls.…”

Section: Macrolactonization and Final Elaboration To (؉)-13-deoxytedamentioning

confidence: 91%

A unified approach to the tedanolides: Total synthesis of (+)-13-deoxytedanolide

Smith

Adams

Barbosa

et al. 2004

Proc. Natl. Acad. Sci. U.S.A.

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A unified approach for the construction of the potent marine antitumor agents (؉)-tedanolide (1) and (؉)-13-deoxytedanolide (2) is described. Highlights of the synthetic strategy include the development of a versatile bifunctional dithiane-vinyl iodide linchpin, the unorthodox use of the Evans-Tishchenko reaction, and a late-stage high-risk stereocontrolled introduction of the C(18,19) epoxide to achieve a total synthesis of (؉)-13-deoxytedanolide (2).

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“…Aldehyde 10 was prepared from 12, readily available in nine steps from methyl (S)-(+)-3-hydroxy-2-methylpropionate by the procedure described by Roush and Lane. [7] Protection of the primary alcohol of 12 as the TBS ether and oxidative cleavage of the olefin furnished aldehyde 10 (Scheme 2). Reaction of the boron enolate of chiral crotonate imide (R)-11 [11] with 10 furnished aldol 13 with excellent stereoselectivity (> 99:1).…”

mentioning

confidence: 82%

“…hand, several syntheses of the C10-C23 region of 5 and 6 have been described [4,[7][8][9] as part of synthetic efforts directed towards the total synthesis of the macrolides. However, a total synthesis of any member of the myriaporone family has not yet been described.…”

mentioning

confidence: 99%

Total Synthesis of Natural Myriaporones

et al. 2004

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Myriaporones 1-4 (1-4, respectively) are a new class of cytotoxic marine polyketide-derived compounds that exhibit significant cytotoxic activity against L1210 cells. These compounds 1-4 were isolated by Rinehart and co-workers in 1995 from the bryozoan Myriapora truncata.[1] The most active constituents, 3 and 4, were isolated as a mixture of cyclic and open-chain isomers. The myriaporones are structurally related to the C10-C23 region of the macrocycles tedanolide (5) [2] and deoxytedanolide (6), [3,4] although the configuration at C5 of 1 and 2 and at C5 and C6 of 3 and 4 were not unequivocally determined. Additionally, the absolute configuration of the myriaporones was unknown. The functionality that flanks the C7 carbonyl group confers significant lability to the myriaporones, which makes these densely functionalized structures challenging synthetic targets. Taylor et al. described progress toward the preparation of myriaporone 1 (1) by a strategy based on an homoallenylboration and a nitrile oxide cycloaddition.[5] Furthermore, Yonemitsu and co-workers reported the synthesis of advanced intermediates from d-glucose.[6] On the other[*] Prof.

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Studies on the Synthesis of Tedanolide. 2. Stereoselective Synthesis of a Protected C(1)−C(12) Fragment

Abstract: [reaction: see text] Highly diastereoselective syntheses of diketo esters 6a and 6b are described. These intermediates undergo efficient aldol reactions with protected C(13)-C(21) aldehydes 3 and 23, thereby providing advanced C(1)-C(21) tedanolide seco ester precursors 9a and 9b.

Cited by 32 publications

References 36 publications

The Synthesis of Desepoxy‐Isotedanolide – A Potential Biosynthetic Precursor of Tedanolide

The Synthesis of Desepoxy‐Isotedanolide – A Potential Biosynthetic Precursor of Tedanolide

A unified approach to the tedanolides: Total synthesis of (+)-13-deoxytedanolide

Total Synthesis of Natural Myriaporones

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