Cyclative Cleavage as a Solid‐Phase Strategy

Ganesan, A.

doi:10.1002/9780470749043.ch4

Cited by 10 publications

(9 citation statements)

References 39 publications

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“…Reaction of 4 { 2 , 1 } with Fmoc-NCS gave the corresponding Fmoc-thiourea 5 { 2 , 1 } which after treatment with DIC, furnished intermediate 6 { 2 , 1 } in excellent crude purity (96%, calculated from LC/UV traces). Cleavage of the Fmoc protecting group was followed by spontaneous intramolecular aminolysis of ester bond and the target product 7 { 2 , 1 } was released from the polymer support by a cyclative cleavage . Separation of the product from the fluorenylmethylpiperidine byproduct formed after Fmoc protecting group removal was easily accomplished by reverse phase semipreparative HPLC.…”

Section: Resultsmentioning

confidence: 99%

“…Cleavage of the Fmoc protecting group was followed by spontaneous intramolecular aminolysis of ester bond and the target product 7{2,1} was released from the polymer support by a cyclative cleavage. 14 Separation of the product from the fluorenylmethylpiperidine byproduct formed after Fmoc protecting group removal was easily accomplished by reverse phase semipreparative HPLC. The model compound 7{2,1} was obtained in a very good overall yield of 45%.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Solid-Phase Synthesis of Anagrelide Sulfonyl Analogues

et al. 2014

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Simple solid-phase synthesis of 3,10-dihydro-2H-benzo[e]imidazo[1,2-b][1,2,4]thiadiazin-2-one 5,5-dioxides is described, with Fmoc-α-amino acids and 2-nitrobenzenesulfonyl chlorides (2-NosCls) being the key building blocks. Fmoc-α-amino acids were immobilized on Wang resin and transformed to the corresponding 2-nitrobenzenesulfonamides in two steps. After reduction of the nitro group, Fmoc-thioureas were synthesized followed by cyclization of the 1,2,4-benzothiadiazine-1,1-dioxide scaffold with diisopropylcarbodiimide (DIC). Cleavage of the Fmoc protecting group followed by spontaneous cyclative cleavage gave the target products in excellent crude purity.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Solid-Phase Synthesis of Anagrelide Sulfonyl Analogues

et al. 2014

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“…Among various synthetic methods to cyclic peptides, the on-resin cyclization approach has been successfully employed in the synthesis of several biologically active natural peptides. Several procedures have been developed for on-resin cyclization in good yields with minimum side products [10][11][12]. For the synthesis of peptide 1, we selected Kenner's sulfonamide safety-catch linker strategy as employed previously for cyclic peptides by others [13][14][15][16] as well as ourselves [17][18][19].…”

Section: Resultsmentioning

confidence: 99%

Total synthesis, structural, and biological evaluation of stylissatin A and related analogs

Shaheen

Jabeen

Ashraf

et al. 2016

Journal of Peptide Science

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ABSTRACT:The natural product cyclic peptide stylissatin A (1a), was reported to inhibit nitric oxide production in LPS-stimulated murine macrophage RAW 264.7 cells. In the current study, solidphase total synthesis of stylissatin A was performed by using a safety-catch linker and yielded the peptide with a trans-Pro 6 -Phe 7 linkage whereas the natural product is the trans rotamer at this position as evidenced by a marked difference in NMR chemical shifts. In order to preclude the possibility of 1b beingan epimer of the natural product, we repeated the synthesis using D-allo- production. The analogues 2-7 weakly inhibited NO . production, but strongly inhibited IL-2 cytokine production compared to synthetic peptide 1b. All analogues inhibited the proliferation of T-cells, with analogue 7 having the strongest effect. In the analogues, the Pro 6 residue was replaced by Glu/Ala and the SAR indicates that the nature of this residue plays a role in the biological function of these peptides.

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“…Judging by the number of reports in this area, cyclative cleavage appears to be the most widely applied strategy for traceless synthesis. Reviews describing this concept have been provided by Tiwari et al, 159 Ganesan, 160,161 and Pernerstorfer. 162 Typically, cyclative cleavage (Scheme 79) involves the intramolecular nucleophilic displacement of a resin-bound ester with an internal nucleophile, causing relesase of a cyclic product.…”

Section: Cyclative Cleavagementioning

confidence: 99%

Section: Cyclative Cleavagementioning

confidence: 99%

Traceless Solid-Phase Organic Synthesis

2019

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Traceless solid-phase synthesis represents an ultimate sophisticated synthetic strategy on insoluble supports. Compounds synthesized on solid supports can be released without a trace of the linker that was used to tether the intermediates during the synthesis. Thus, the target products are composed only of the components (atoms, functional groups) inherent to the target core structure. A wide variety of synthetic strategies have been developed to prepare products in a traceless manner, and this review is dedicated to all aspects of traceless solid-phase organic synthesis. Importantly, the synthesis does not need to be carried out on a linker designed for traceless synthesis; most of the synthetic approaches described herein were developed using standard, commercially available linkers (originally devised for solid-phase peptide synthesis). The type of structure prepared in a traceless fashion is not restricted. The individual synthetic approaches are divided into eight sections, each devoted to a different methodology for traceless synthesis. Each section consists of a brief outline of the synthetic strategy followed by a description of individual reported syntheses.

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Cyclative Cleavage as a Solid‐Phase Strategy

Cited by 10 publications

References 39 publications

Solid-Phase Synthesis of Anagrelide Sulfonyl Analogues

Solid-Phase Synthesis of Anagrelide Sulfonyl Analogues

Total synthesis, structural, and biological evaluation of stylissatin A and related analogs

Traceless Solid-Phase Organic Synthesis

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