Synthesis of the hexacyclic triterpene core of the jujuboside saponins via tandem Wolff rearrangement–intramolecular ketene hetero-Diels–Alder reaction

Karimov, Rashad R.; Tan, Derek S.; Gin, David Y.

doi:10.1016/j.tet.2018.04.051

Cited by 10 publications

(7 citation statements)

References 60 publications

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“…The novel saponin–tucaresol conjugates showed robust adjuvanticity and low toxicity which contributed to further studies on QS conjugation . Plentiful strategies for facile saponin synthesis have been reported. , For example, sterically hindered glycosylation was carried out with B(C 6 F 5 ) 3 catalysis. Compared to the conventional catalysis method, the trisaccharide and disaccharide subunits were joined with the late-stage coupling method, displaying a more rapid synthesis strategy .…”

Section: Adjuvants For Enhancing Vaccinationmentioning

confidence: 99%

Chemical Strategies to Boost Cancer Vaccines

2020

Chem. Rev.

120

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Personalized cancer vaccines (PCVs) are reinvigorating vaccine strategies in cancer immunotherapy. In contrast to adoptive T-cell therapy and checkpoint blockade, the PCV strategy modulates the innate and adaptive immune systems with broader activation to redeploy antitumor immunity with individualized tumor-specific antigens (neoantigens). Following a sequential scheme of tumor biopsy, mutation analysis, and epitope prediction, the administration of neoantigens with synthetic long peptide (SLP) or mRNA formulations dramatically improves the population and activity of antigen-specific CD4+ and CD8+ T cells. Despite the promising prospect of PCVs, there is still great potential for optimizing prevaccination procedures and vaccine potency. In particular, the arduous development of tumor-associated antigen (TAA)-based vaccines provides valuable experience and rational principles for augmenting vaccine potency which is expected to advance PCV through the design of adjuvants, delivery systems, and immunosuppressive tumor microenvironment (TME) reversion since current personalized vaccination simply admixes antigens with adjuvants. Considering the broader application of TAA-based vaccine design, these two strategies complement each other and can lead to both personalized and universal therapeutic methods. Chemical strategies provide vast opportunities for (1) exploring novel adjuvants, including synthetic molecules and materials with optimizable activity, (2) constructing efficient and precise delivery systems to avoid systemic diffusion, improve biosafety, target secondary lymphoid organs, and enhance antigen presentation, and (3) combining bioengineering methods to innovate improvements in conventional vaccination, "smartly" re-educate the TME, and modulate antitumor immunity. As chemical strategies have proven versatility, reliability, and universality in the design of T cell-and B cell-based antitumor vaccines, the union of such numerous chemical methods in vaccine construction is expected to provide new vigor and vitality in cancer treatment.

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Section: Adjuvants For Enhancing Vaccinationmentioning

confidence: 99%

Chemical Strategies to Boost Cancer Vaccines

2020

Chem. Rev.

120

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“…Our synthesis began with ketone 10, a derivative of the enantiomerically pure Wieland-Miescher ketone. [15] Reactions including methylation, trifluoromethanesulfonylation and allylic oxidation gave compound 11 in 64 % yield over three steps. [16] Burke's building block was then utilized to efficiently construct the precursor of the 6π-electrocyclization reaction, [17] giving 13 in 61 % yield over three steps.…”

Section: Resultsmentioning

confidence: 99%

Synthesis towards Phainanoid F: Photo‐induced 6π‐Electrocyclization for Constructing Contiguous All‐Carbon Quaternary Centers

Liu,

Zhang,

Zhou

et al. 2023

Chemistry An Asian Journal

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In this paper, we report an efficient strategy for synthesizing the DEFGH rings of phainanoid F. The key to the construction of the 13,30‐cyclodammarane skeleton of the molecule was a photo‐induced 6π‐electrocyclization and a homoallylic elimination. Notably, this is a rare example of using electrocyclization reaction to simultaneously construct two vicinal quaternary carbons in total synthesis. The strategy outlined here forms the basis of our total synthesis of Phainanoid F, and it could also serve as a generally applicable approach for synthesizing other natural products containing the 13,30‐cyclodammarane skeleton.

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“…Acid catalyzed cyclization of the resulting bicyclic enol ether then closed the E-ring to provide the hexacyclic core of jujubogenin (216) (Scheme 23). 55 Diene 203 was obtained by the addition of vinylmagnesium bromide followed by dehydration starting from ketone 202, which was prepared from Wieland-Miescher ketone (1) in 7 steps (Scheme 23). The Diels-Alder reaction was carried out skeleton and displays weak cytotoxic activity against HeLa, HepG2, and SGC-7901 cancer cell lines.…”

Section: (Scheme 16)mentioning

confidence: 99%

“…Acid catalyzed cyclization of the resulting bicyclic enol ether then closed the E-ring to provide the hexacyclic core of jujubogenin ( 216 ) (Scheme 23). 55…”

mentioning

confidence: 99%