Synthetic Studies on Thiostrepton: Construction of Thiostrepton Analogues with the Thiazoline‐Containing Macrocycle

Nicolaou, K. C.; Nevalainen, Marta; Zak, Mark; Bulat, Stephan; Bella, Marco; Safina, Brian S.

doi:10.1002/ange.200351745

Cited by 46 publications

(49 citation statements)

References 23 publications

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“…The allyl ester group was then removed from the isoleucine residue by palladium-catalyzed reductive cleavage, [8] which gave rise to the corresponding carboxylic acid 20 in good yield. Coupling of 20 with dipeptide 8 (Scheme 1) under established conditions generated quinaldic acid derivative 21 ( 3 SnH liberated the targeted carboxylic acid 22 in 87 % yield, ready for incorporation into the growing frame of 1.…”

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“…Thus, 9 was converted in five steps and good overall yield as previously described [3] into functionalized methyl ester 10. The latter compound was then oxygenated to afford 11 in 65 % overall yield through a Boekelheide-type sequence [4] involving a) MCPBA-mediated N-oxide formation; b) TFAA-induced acylation of the generated N-oxide; and c) NaHCO 3 -facilitated rearrangement-hydrolysis of the resulting trifluoroacetate.…”

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Total Synthesis of Thiostrepton, Part 2: Construction of the Quinaldic Acid Macrocycle and Final Stages of the Synthesis

et al. 2004

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In the preceding Communication in this issue [1] we described the construction of the thiazoline-containing macrocycle 2 as an advanced intermediate toward the total synthesis of thiostrepton (1). Herein we report the construction of suitable dipeptide (8, Scheme 1) and quinaldic acid (22, Scheme 2) fragments, their union with 2, and the final stages of the total synthesis of 1.Scheme 1 outlines the synthesis of the required dipeptide derivative 8 from 3, a known phenylseleno-substituted derivative of alanine.[2] Thus, 3 was converted into allyl ester 4, which was treated with TFA to effect its conversion into the amino derivative 5. Coupling of amine 5 with Boc-l-alanine

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Total Synthesis of Thiostrepton, Part 2: Construction of the Quinaldic Acid Macrocycle and Final Stages of the Synthesis

et al. 2004

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“…The allyl ester group was then removed from the isoleucine residue by palladium-catalyzed reductive cleavage, [8] which gave rise to the corresponding carboxylic acid 20 in good yield. Coupling of 20 with dipeptide 8 (Scheme 1) under established conditions generated quinaldic acid derivative 21 (Table 1) 3 SnH liberated the targeted carboxylic acid 22 in 87 % yield, ready for incorporation into the growing frame of 1.…”

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“…Advanced thiazoline macrocycle 2 [1] was treated with Me 3 SnOH [9] in 1,2-dichloroethane at 65 8C to liberate carboxylic acid 23, which was coupled with the bisphenylselenium tail derivative 24 (prepared as previously described) [10] under the influence of HATU-HOAt to afford intermediate 25 ( [8] cleaved its Alloc group and furnished primary amine 26 in 86 % yield in preparation for the incorporation of 22. Indeed, coupling of amino compound 26 with carboxylic acid 22 was effected once again with HATU-HOAt, leading to polypeptide 27 (Table 1) in 64 % yield.…”

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Total Synthesis of Thiostrepton, Part 2: Construction of the Quinaldic Acid Macrocycle and Final Stages of the Synthesis

et al. 2004

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In the preceding Communication in this issue [1] we described the construction of the thiazoline-containing macrocycle 2 as an advanced intermediate toward the total synthesis of thiostrepton (1). Herein we report the construction of suitable dipeptide (8, Scheme 1) and quinaldic acid (22, Scheme 2) fragments, their union with 2, and the final stages of the total synthesis of 1.Scheme 1 outlines the synthesis of the required dipeptide derivative 8 from 3, a known phenylseleno-substituted derivative of alanine. [2] Thus, 3 was converted into allyl ester 4, which was treated with TFA to effect its conversion into the amino derivative 5. Coupling of amine 5 with Boc-l-alanine

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A Facile Synthesis of 1,5‐Disubstituted Tetrazole Peptidomimetics by Desulfurization/Electrocyclization of Thiopeptides

et al. 2015

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The cis-amide bond isostere, 1,5-disubstituted tetrazole,has been introduced in the peptideb ackbone by as imple route startingf rom the thiopeptide. The desired 1,5-disubstituted tetrazole peptidomimetics were synthesized by the desulfurization of thiopeptides by using HgCl 2 in the presence of NaN 3 /TEA in DMF in good yields. Various other thiophilic reagents including hypervalent iodine reagents failed to deliver the tetrazole product with the exception of CBr 4 /PPh 3 ,w hich resulted in moderate yields. The advantage of the presentp rotocol over previousm ethods has been demonstrated by the selective insertion of tetrazole into peptide-thiopeptide hybrids. Also, the protocol is compatible with commonly employed urethane protecting groups (Fmoc, Boc, and Cbz) in peptidec hemistry.T hiopeptide Boc-Pro-y[CSNH]-Val-OMe (2i)a nd two tetrazole pepti-domimeticsC bz-Ala-y[CN 4 ]-Phe-OMe( 3d)a nd Boc-Proy[CN 4 ]-Val-OMe( 3i)w ere obtained as single crystalsa nd their molecular structures have been confirmed by X-ray crystallography.

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Synthetic Studies on Thiostrepton: Construction of Thiostrepton Analogues with the Thiazoline‐Containing Macrocycle

Abstract: Beispielhaft: Makrolactamisierungen sind die Schlüsselschritte in den Synthesen des neuartigen Thiostrepton‐Analogons 1 und seines 5S,6S‐Diastereomers. Diese Vorgehensweise bietet sich auch für die Synthese des eigentlichen Naturstoffs an.

Cited by 46 publications

References 23 publications

Total Synthesis of Thiostrepton, Part 2: Construction of the Quinaldic Acid Macrocycle and Final Stages of the Synthesis

Total Synthesis of Thiostrepton, Part 2: Construction of the Quinaldic Acid Macrocycle and Final Stages of the Synthesis

Total Synthesis of Thiostrepton, Part 2: Construction of the Quinaldic Acid Macrocycle and Final Stages of the Synthesis

A Facile Synthesis of 1,5‐Disubstituted Tetrazole Peptidomimetics by Desulfurization/Electrocyclization of Thiopeptides

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