56691-80-6Relevant academic research and scientific papers
Synthesis from geraniol of (2E,6E,10E,14E)-16-hydroxygeranylgeraniol and some of its derivatives
Grin'ko,Kulcitki,Ungur,Barba,Delyanu,Vlad
, p. 277 - 281 (2007)
Several α,ω-bifunctional derivatives of E,E,E-geranylgeraniol were prepared via convergent synthesis starting with geraniol (8), which was converted in three steps into the tetrahydropyranyl ether of 8-chlorogeraniol (9) and 8-hydroxygeranylphenylsulfone (10). Combination of synthons 9 and 10 with subsequent reductive removal of the phenylsulfonyl group produced the tetrahydropyranyl ether of ω-hydroxygeranylgeraniol (5), hydrolysis of which gave exclusively trans-ω-hydroxygeranylgeraniol (1). Derivatives 5-7 of geranylgeraniol were synthesized using standard methods.
Palladium-catalyzed substitution of allylic alcohols with sulfinate salts: A synthesis of bicalutamide
Jhang, Yin-Jia,Chang, Chieh-Yu,Lin, Yu-Huan,Lee, Chein-Chung,Wu, Yen-Ku
supporting information, (2021/05/04)
A method is presented for the direct substitution of allylic alcohols with sodium arylsulfinates. The process involves a cooperative action of palladium catalysts, phenylboronic acid and titanium tetraisopropoxide. By taking advantage of this protocol, we achieved a concise synthesis of bicalutamide, an anti-androgen compound for treating prostate cancer.
Rh2(II)-Catalyzed intermolecular N-Aryl aziridination of olefins using nonactivated N atom precursors
Deng, Tianning,Mazumdar, Wrickban,Yoshinaga, Yuki,Patel, Pooja B.,Malo, Dana,Malo, Tala,Wink, Donald J.,Driver, Tom G.
supporting information, p. 19149 - 19159 (2021/11/23)
The development of the first intermolecular Rh2(II)-catalyzed aziridination of olefins using anilines as nonactivated N atom precursors and an iodine(III) reagent as the stoichiometric oxidant is reported. This reaction requires the transfer of an N-aryl nitrene fragment from the iminoiodinane intermediate to a Rh2(II) carboxylate catalyst; in the absence of a catalyst only diaryldiazene formation was observed. This N-aryl aziridination is general and can be successfully realized by using as little as 1 equiv of the olefin. Di-, tri-, and tetrasubstituted cyclic or acylic olefins can be employed as substrates, and a range of aniline and heteroarylamine N atom precursors are tolerated. The Rh2(II)-catalyzed N atom transfer to the olefin is stereospecific as well as chemo- and diastereoselective to produce the N-aryl aziridine as the only amination product. Because the chemistry of nonactivated N-aryl aziridines is underexplored, the reactivity of N-aryl aziridines was explored toward a range of nucleophiles to stereoselectively access privileged 1,2-stereodiads unavailable from epoxides, and removal of the N-2,4-dinitrophenyl group was demonstrated to show that functionalized primary amines can be constructed.
CHINONE-, HYDROCHINOME- AND NAPHTHOCHINONE-ANALOGUES OF VATIQUIONE FOR TREATMENT OF MITOCHONDRIAL DISORDER DISEASES
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Page/Page column 212-213, (2021/04/10)
The disclosure provides therapeutic compositions (i.e., therapeutic agents) and methods of preventing or treating Friedreich's ataxia in a mammalian subject, reducing risk factors, signs and/or symptoms associated with Friedreich's ataxia (e.g. Complex I deficiency), and/or reducing the likelihood or severity of Friedreich's ataxia. The disclosure further provides novel intermediates for the production of said therapeutic compositions and related reduced versions of said therapeutic compositions, which reduce forms may also be used as therapeutic agents (or prodrugs of the therapeutic agent(s)).
Methyl-Shifted Farnesyldiphosphate Derivatives Are Substrates for Sesquiterpene Cyclases
Harms, Vanessa,Schr?der, Benjamin,Oberhauser, Clara,Tran, Cong Duc,Winkler, Sven,Dr?ger, Gerald,Kirschning, Andreas
supporting information, p. 4360 - 4365 (2020/06/08)
New sesquiterpene backbones are accessible after biotransformation of presilphiperfolan-8β-ol synthase (BcBOT2), a fungal sesquiterpene synthase, with non-natural farnesyldiphosphates in which methyl groups are shifted by one position toward the diphosphate terminus. One of the macrocycles formed, a new germacrene A derivative, undergoes a Cope rearrangement to iso-β-elemene. Three of the new terpenoids show olfactoric properties that range from an intense peppery note to a citrus, ozone-like, and fruity scent.
PROCESS OF VITAMIN K2 DERIVATIVES PREPARATION
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Page/Page column 24; 25, (2019/10/29)
Provided is an improved process of vitamin K2 derivatives preparation, represented by formula (I) wherein n is an integer from 3 to 13.
Squalene-Hopene Cyclase: On the Polycyclization Reactions of Squalene Analogues Bearing Ethyl Groups at Positions C-6, C-10, C-15, and C-19
Takahashi, Kazunari,Sasaki, Yusuke,Hoshino, Tsutomu
supporting information, p. 1477 - 1490 (2018/04/06)
Squalene-hopene cyclase (SHC) has been found to convert acyclic squalene into 6,6,6,6,5-fused pentacyclic triterpenes hopene and hopanol. The enzymatic reactions of squalene analogues bearing ethyl groups in lieu of methyl groups at positions C-6, C-10, C-15, and C-19 have been examined to investigate whether the larger ethyl substituents (a C1 unit increment) are accepted as substrates and to investigate how these substitutions affect polycyclization cascades. Analogue 6-ethylsqualene 19a did not cyclize, which indicates that substitution with the bulky group at C-6 completely inhibited the polycyclization reaction. In contrast, 19-ethylsqualene 19b afforded a wide spectrum of cyclization products, including mono-, bi-, tetra-, and pentacyclic products in a ratio of 6:6:1:2. The production of tetra- and pentacyclic scaffolds suggests that the reaction cavity for D-ring formation site is somewhat loosely packed and can accept the 19-ethyl group, and that a robust hydrophobic interaction exists between the 19-ethyl group and the binding site. In contrast to 19b, 10-ethylsqualene 20a and 15-ethylsqualene 20b afforded mainly mono- and bicyclic products, that is, the polycyclization cascade terminated prematurely at the bicyclic reaction stage. Therefore, the catalytic domains for the 10- and 15-methyl binding sites are tightly packed and cannot fully accommodate the Et substituents. The cyclization pathways followed by the ethyl-substituted substrates in the presence of SHC and lanosterol and β-amyrin synthases are compared.
Reactivity of 2-Nitropyrrole Systems: Development of Improved Synthetic Approaches to Nitropyrrole Natural Products
Ding, Xiao-Bo,Brimble, Margaret A.,Furkert, Daniel P.
, p. 12460 - 12470 (2018/10/20)
Fundamental study of the reactivity of 2-nitropyrrole systems has enabled the identification of effective methods for incorporation of this unusual motif into advanced natural product frameworks. The presence of electron-rich pyrrole N-protecting groups (BOM, Boz) was demonstrated to enable a variety of previously unsuccessful palladium-mediated cross-couplings to be carried out in high yield. Based on this foundation, a series of regio- and stereoselective synthetic routes toward the nitropyrrolin and heronapyrrole families of natural products was developed by our group (G1-3). A full account of the strategic evolution of these approaches is reported here, highlighting the details of the setbacks encountered and eventual successes achieved en route, including the total synthesis of heronapyrrole B. The fundamental studies and completed total syntheses provide general access to the bioactive 2-nitropyrrole natural product manifold and also establish practical and efficient methods for preparation and elaboration of the medicinally relevant 2-nitropyrrole motif.
Development of a new air-stable structure-simplified nafuredin-γ analog as a potent and selective nematode complex I inhibitor
Ohtawa, Masaki,Arima, Shiho,Shimizu, Risa,Hanatani, Naomi,Shimizu, Eri,Shiomi, Kazuro,Kita, Kiyoshi,ōmura, Satoshi,Nagamitsu, Tohru
, p. 647 - 654 (2017/05/29)
Nafuredin-γ, obtained from natural nafuredin, has demonstrated a potent and selective inhibitory activity against nematode complex I. However, nafuredin-γ is unstable in air since its conjugated dienes are oxygen-labile. The instability in air was natural
β-Amyrin Biosynthesis: Effect of Steric Bulk at the 6-, 10- and 15-Positions in the 2,3-Oxidosqualene Backbone on Polycyclisation Cascades
Terasawa, Yuri,Sasaki, Yusuke,Yamaguchi, Yuki,Takahashi, Kazunari,Hoshino, Tsutomu
supporting information, p. 287 - 295 (2017/01/24)
β-Amyrin synthase incubation experiments have been conducted to determine the influence of steric effects at the 6-, 10- and 15-positions of 2,3-oxidosqualene on the polycyclisation pathway. Nor- and ethyl-substituted oxidosqualene analogues were synthesised. Cyclisation of the ethyl-substituted analogues did not occur, but the nor analogues underwent a polycyclisation cascade to yield fully cyclised products with 6/6/6/6/6-fused pentacyclic scaffolds generated via a final oleanyl cation. Previously, we reported that 19- and 23-ethyl-substituted analogues underwent polycyclisation reactions. Therefore, the catalytic domain involved in earlier cyclisation steps is notably compact. In contrast, the catalytic domain in the later cyclisation steps is more loosely packed (less compact) to accommodate the bulky ethyl group. The reaction cavities for recognising branched methyl groups are discussed by comparing β-amyrin synthase with other triterpene cyclases such as lanosterol and hopene synthases.
