- Novel broccoli sulforaphane-based analogues inhibit the progression of pancreatic cancer without side effects
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The naturally occurring isothiocyanate sulforaphane, found in Brassicaceae vegetables, is promising in cancer treatment, e.g., by the normalization of enhanced levels of NF-κB-signaling in tumor stem cells. We chemically synthesized seven sulforaphane ana
- Bolm, Carsten,Bremerich, Maximilian,Buglioni, Laura,Georgikou, Christina,Gross, Wolfgang,Herr, Ingrid,Roubicek, Nico,Sticht, Carsten,Yin, Libo
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- Synthesis and bioactivity of 4-methylthio-3-butenylisothiocyanate and raphanusanin, phototropism-regulating substances of radish hypocotyls
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Total syntheses of 4-methylthio-3-butenylisothiocyanate (MTBI, 1) and raphanusanin (2), which are growth inhibitors involved in the phototropism of radish (Raphanus sativus) hypocotyls, were achieved from commercially available thiolane in four and five steps, respectively. MTBI (1) was prepared via the ring opening of thiolane with sodium azide, double bond introduction by oxidation, and isothiocyanation. Cyclization of MTBI to raphanusanin (2) was achieved under mild conditions using sauer Al2O3. Synthetic MTBI (1) and raphanusanin (2) showed potent bioactivity in a unilateral administration test and a segment elongation test using radish hypocotyls.
- Noguchi, Yoshiki,Watanabe, Ryoko,Arai, Atsushi,Yamada, Kosumi,Hasegawa, Koji,Horinouchi, Taeko,Watanabe, Hidenori,Shigemori, Hideyuki
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- Chemical synthesis method for sulforaphane
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The invention discloses a chemical synthesis method for sulforaphane. The method is characterized by including the steps of: (a) taking sodium iodide as the catalyst, reacting 4-chloro-1-butanol with sodium methyl mercaptide to obtain 4-methylthio-1-butanol; (b) in the presence of alkali, reacting 4-methylthio-1-butanol with methylsufonyl chloride to obtain 4-methylthio-1-butylmethysulfonate; (c) reacting4-methylthio-1-butylmethysulfonate with sodium azide in the presence of a phase transfer catalyst to obtain 1-azido-4-methylthiobutane; (d) reacting 1-azido-4-methylthiobutane with triphenylphosphine, and then carrying out reaction with carbon disulfide under a room temperature condition to obtain 1-isothiocyano-4-methylthiobutane; and (e) oxidizing1-isothiocyano-4-methylthiobutane with m-CPBA under a low temperature condition to obtain sulforaphane. The method provided by the invention has the advantages of simple technological process, easy treatment and high total yield (75%), and can achieve effective large-scale production of sulforaphane.
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Paragraph 0015
(2017/11/16)
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- A new and effective approach to the synthesis of sulforaphane
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Background: Sulforaphane [1-isothiocyanato-(4-methylsulfinyl)butane] identified from appears to possess health benefits such as activities against breast, skin and prostate cancer and diabetes. and studies provide evidence that it can provide protection at every stage of cancer progression. Sulforaphane was firstly synthesized by Von Schmidt and P.Karrer in 1948 via phthalimide route but after Zhang and co-worker reported its bioactivity in 1992, the chemical synthesis of sulforaphane by alternate route has attracted several research groups in the past 20 years . Methods: The synthesis started with the preparation of-methylthiolanium tetrafluoroborate by sonication of thiolane (1) with methyl iodide followed by anionic metathesis with NaBF4 in-butanol to give thiolanium tetrafluorborate (2). The ring opening of 2 by SN2 is conducted in 16 hours at 60 oC (as indicated by TLC) to obtain 1-Azido-(4-methylsulfinyl)butane (3). Conversion 3 into Erucin (4) was successfully obtained by Staudinger reaction, followed by oxidation of 4 in transition metal-free condition (H2O2/ glacial acetic acid) to give sulforaphane in racemic form. Results: Sulforaphane was obtained with 41% yield overall via only four steps with high purity without column chromatography. The approach not only opened up a new synthetic pathway to this naturally occurring isothiocyanate and its analogues, but also suggested a possible solution for converting by-products in petroleum refining processes into useful compounds. Conclusion: Sulforaphane was successfully synthesized from thiolane, a waste product in petroleum processing in a simpler and more efficient fashion, eco-friendy approach. All products were obtained in high yield and high purity. In comparison with previously reported strategies, this new approach is believed to be the shortest and the most efficient synthetic route to date.
- Vo, Duy-Viet,Truong, Van-Dat,Tran, Thanh-Dao,Do, Van-Thanh-Nhan,Pham, Ngoc-Tuan-Anh,Thai, Khac-Minh
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- A new and effective approach to the synthesis of sulforaphane
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Background: Sulforaphane [1-isothiocyanato-(4-methylsulfinyl)butane] identified from Brassicaceae appears to possess health benefits such as activities against breast, skin and prostate cancer and diabetes. In vitro and vivo studies provide evidence that it can provide protection at every stage of cancer progression. Sulforaphane was firstly synthesized by Von Schmidt and P.Karrer in 1948 via phthalimide route but after Zhang and co-worker reported its bioactivity in 1992, the chemical synthesis of sulforaphane by alternate route has attracted several research groups in the past 20 years. Methods: The synthesis started with the preparation of S-methylthiolanium tetrafluoroborate by sonication of thiolane (1) with methyl iodide followed by anionic metathesis with NaBF4 in n-butanol to give thiolanium tetrafluorborate (2). The ring opening of 2 by SN2 is conducted in 16 hours at 60 °C (as indicated by TLC) to obtain 1-azido-(4-methylsulfinyl)butane (3). Conversion 3 into Erucin (4) was successfully obtained by Staudinger reaction, followed by oxidation of 4 in transition metal-free condition (H2O2/glacial acetic acid) to give sulforaphane in racemic form. Results: Sulforaphane was obtained with 41% yield overall via only four steps with high purity without column chromatography. The approach not only opened up a new synthetic pathway to this naturally occurring isothiocyanate and its analogues, but also suggested a possible solution for converting by-products in petroleum refining processes into useful compounds. Conclusion: Sulforaphane was successfully synthesized from thiolane, a waste product in petroleum processing in a simpler and more efficient fashion, eco-friendy approach. All products were obtained in high yield and high purity. In comparison with previously reported strategies, this new approach is believed to be the shortest and the most efficient synthetic route to date.
- Vo, Duy-Viet,Truong, Van-Dat,Tran, Thanh-Dao,Do, Van-Thanh-Nhan,Pham, Ngoc-Tuan-Anh,Thai, Khac-Minh
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- Sulforaphane and erucin, natural isothiocyanates from broccoli, inhibit bacterial quorum sensing
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Sulforaphane and erucin, two natural isothiocyanates that are highly abundant in broccoli and other cruciferous vegetables, were found to strongly inhibit quorum sensing and virulence in Pseudomonas aeruginosa. Mechanistic evaluations of these effects suggest that these isothiocyanates are antagonists of the transcriptional activator LasR. The Royal Society of Chemistry 2013.
- Ganin, Hadas,Rayo, Josep,Amara, Neri,Levy, Niva,Krief, Pnina,Meijler, Michael M.
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p. 175 - 179
(2013/03/13)
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- A SIMPLE, BIOGENETICALLY MODELED SYNTHESIS OF 4-(METHYLTHIO)BUTYL THIOCYANATE: THE REACTION OF THIOCYANATE ANION WITH S-METHYL-(1,n)-EPITHIONIUM IONS
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The reaction of S-methylthiolanium fluorosulphate with thiocyanate ion gives predominantly 4-(methylthio)butyl thiocyanate, a result which is in accord with a hypothesis for the biogenesis of this compound, and which has implications for the natural occurrence of analogous thiocyanates.
- Benn, M. H.,Singh, Vinod K.
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p. 940 - 942
(2007/10/02)
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