464-45-9Relevant academic research and scientific papers
Enantioselective Construction of Modular and Asymmetric Baskets
Badji?, Jovica D.,Finnegan, Tyler J.,Gunther, Michael J.,Pavlovi?, Radoslav Z.,Wang, Xiuze
supporting information, p. 25075 - 25081 (2021/10/25)
The precise positioning of functional groups about the inner space of abiotic hosts is a challenging task and of interest for developing more effective receptors and catalysts akin to those found in nature. To address it, we herein report a synthetic methodology for preparing basket-like cavitands comprised of three different aromatics as side arms with orthogonal esters at the rim for further functionalization. First, enantioenriched A (borochloronorbornene), B (iodobromonorbornene), and C (boronorbornene) building blocks were obtained by stereoselective syntheses. Second, consecutive A-to-B and then AB-to-C Suzuki–Miyaura (SM) couplings were optimized to give enantioenriched ABC cavitand as the principal product. The robust synthetic protocol allowed us to prepare (a) an enantioenriched basket with three benzene sides and each holding either tBu, Et, or Me esters, (b) both enantiomers of a so-called “spiral staircase” basket with benzene, naphthalene, and anthracene groups surrounding the inner space, and (c) a photo-responsive basket bearing one anthracene and two benzene arms.
Simple Plug-In Synthetic Step for the Synthesis of (?)-Camphor from Renewable Starting Materials
Calderini, Elia,Drienovská, Ivana,Myrtollari, Kamela,Pressnig, Michaela,Sieber, Volker,Schwab, Helmut,Hofer, Michael,Kourist, Robert
, p. 2951 - 2956 (2021/06/18)
Racemic camphor and isoborneol are readily available as industrial side products, whereas (1R)-camphor is available from natural sources. Optically pure (1S)-camphor, however, is much more difficult to obtain. The synthesis of racemic camphor from α-pinene proceeds via an intermediary racemic isobornyl ester, which is then hydrolyzed and oxidized to give camphor. We reasoned that enantioselective hydrolysis of isobornyl esters would give facile access to optically pure isoborneol and camphor isomers, respectively. While screening of a set of commercial lipases and esterases in the kinetic resolution of racemic monoterpenols did not lead to the identification of any enantioselective enzymes, the cephalosporin Esterase B from Burkholderia gladioli (EstB) and Esterase C (EstC) from Rhodococcus rhodochrous showed outstanding enantioselectivity (E>100) towards the butyryl esters of isoborneol, borneol and fenchol. The enantioselectivity was higher with increasing chain length of the acyl moiety of the substrate. The kinetic resolution of isobornyl butyrate can be easily integrated into the production of camphor from α-pinene and thus allows the facile synthesis of optically pure monoterpenols from a renewable side-product.
Monoterpenoid-based inhibitors of filoviruses targeting the glycoprotein-mediated entry process
Baev, Dmitriy S.,Maksyutov, Rinat A.,Mordvinova, Ekaterina D.,Pyankov, Oleg V.,Salakhutdinov, Nariman F.,Shcherbakov, Dmitriy N.,Shcherbakova, Nadezhda S.,Sokolova, Anastasiya S.,Tolstikova, Tatyana G.,Yarovaya, Olga I.,Zaykovskaya, Anna V.,Zybkina, Anastasiya V.
, (2020/09/09)
In this study, we screened a large library of (+)-camphor and (?)-borneol derivatives to assess their filovirus entry inhibition activities using pseudotype systems. Structure-activity relationship studies revealed several compounds exhibiting submicromolar IC50 values. These compounds were evaluated for their effect against natural Ebola virus (EBOV) and Marburg virus. Compound 3b (As-358) exhibited the good antiviral potency (IC50 = 3.7 μM, SI = 118) against Marburg virus, while the hydrochloride salt of this compound 3b·HCl had a strong inhibitory effect against Ebola virus (IC50 = 9.1 μM, SI = 31) and good in vivo safety (LD50 > 1000 mg/kg). The results of molecular docking and in vitro mutagenesis analyses suggest that the synthesized compounds bind to the active binding site of EBOV glycoprotein similar to the known inhibitor toremifene.
Molecular cloning and functional characterization of a two highly stereoselective borneol dehydrogenases from Salvia officinalis L
Drienovská, Ivana,Kolanovi?, Dajana,Chánique, Andrea,Sieber, Volker,Hofer, Michael,Kourist, Robert
, (2020/01/11)
Enzymes for selective terpene functionalization are of particular importance for industrial applications. Pure enantiomers of borneol and isoborneol are fragrant constituents of several essential oils and find frequent application in cosmetics and therapy. Racemic borneol can be easily obtained from racemic camphor, which in turn is readily available from industrial side-streams. Enantioselective biocatalysts for the selective conversion of borneol and isoborneol stereoisomers would be therefore highly desirable for their catalytic separation under mild reaction conditions. Although several borneol dehydrogenases from plants and bacteria have been reported, none show sufficient stereoselectivity. Despite Croteau et al. describing sage leaves to specifically oxidize one borneol enantiomer in the late 70s, no specific enzymes have been characterized. We expected that one or several alcohol dehydrogenases encoded in the recently elucidated genome of Salvia officinalis L. would, therefore, be stereoselective. This study thus reports the recombinant expression in E. coli and characterization of two enantiospecific enzymes from the Salvia officinalis L. genome, SoBDH1 and SoBDH2, and their comparison to other known ADHs. Both enzymes produce preferentially (+)-camphor from racemic borneol, but (?)-camphor from racemic isoborneol.
Synthesis method of levo-borneol
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Paragraph 0036; 0039-0041; 0044-0046; 0049-0051; 0054-0055, (2020/09/02)
The invention relates to a synthetic method of L-borneol. The method comprises: reducing di-n-butyltin dichloride to obtain di-n-butyltin dihydride via lithium aluminium hydride, performing a reactionamong 2-camphanone, palladium bis(triphenylphosphine) dichloride and methanol, adding di-n-butyltin dihydride drop by drop while performing uniform stirring, performing a reaction at the room temperature for 1 h, after the reaction is over, performing pressure-reduction rotary evaporation to remove methanol, and performing separation to obtain L-borneol, which is the target compound.
Alkane-, alkene-, alkyne-γ-lactones and ryanodane diterpenes from aeroponically grown Persea indica roots
Fraga, Braulio M.,Díaz, Carmen E.,Bola?os, Patricia,Bailén, María,Andrés, María Fe,González-Coloma, Azucena
, (2020/05/25)
This work presents the study of the roots of the Macaronesian paleoendemism Persea indica (L.) Spreng. The root biomass of this protected tree species has been produced by soil-less aeroponic culture under controlled environment. This system has important advantages over traditional plant production techniques because it provides opportunities to optimize the yield of metabolite production under well-controlled conditions, thereby facilitating commercial-scale production of bioactive compounds. Thus, for the first time a study of this type has permitted the isolation from the roots of seven undescribed dextrorotatory lactones: the alkane-γ-lactones (+)-majoranolide and (+)-dihydromajorenolide, the alkene-γ-lactones (+)-majorenolide and (+)-majorenolide acetate, and the alkyne-γ-lactones, (+)-majorynolide, (+)-majorynolide acetate and (+)-isomajorynolide. In addition, thirteen known compounds were also isolated including two possible avocadofurane precursors, avocadynone acetate and avocadenone acetate, the monoterpene esters cis- and trans-p-coumarate of (?)-borneol, and the ryanoid diterpenes cinnzeylanone, anhidrocinnzeylanine, cinnzeylanine, cinnzeylanol, epiryanodol, perseanol, cinncassiol E, perseaindicol and secoperseanol. The configuration at C-14 de two ryanodane diterpenes has also been revised in this work. Furthermore, (?)-borneol cis-p-coumarate has showed to be insecticidal to S. littoralis and cytotoxic to insect (Sf9) cells, (+)-majorenolide antifeedant to aphids and cytotoxic to Sf9, cinnceylanol antifeedant and insecticidal to S. littoralis, and (+)-majorynolide (2), insecticidal against S. littoralis, cytotoxic to Sf9 and nematicidal, suggesting a defensive role for these compounds.
One-Pot Absolute Stereochemical Identification of Alcohols via Guanidinium Sulfate Crystallization
Brummel, Beau R.,Lee, Kinsey G.,McMillen, Colin D.,Kolis, Joseph W.,Whitehead, Daniel C.
, p. 9622 - 9627 (2019/12/02)
A novel technique for the absolute stereochemical determination of alcohols has been developed that uses crystallization of guanidinium salts of organosulfates. The simple one-pot, two-step process leverages facile formation of guandinium organosulfate single crystals for the straightforward determination of the absolute stereochemistry of enantiopure alcohols by means of X-ray crystallography. The strong hydrogen bonding network drives the stability of the crystal lattice and allows for a diverse range of organic alcohol substrates to be analyzed.
Hydrogen Sulfide: A Reagent for pH-Driven Bioinspired 1,2-Diol Mono-deoxygenation and Carbonyl Reduction in Water
Barata-Vallejo, Sebastián,Ferreri, Carla,Golding, Bernard T.,Chatgilialoglu, Chryssostomos
supporting information, p. 4290 - 4294 (2018/07/29)
Hydrogen sulfide (H2S) was evaluated for its peculiar sulfur radical species generated at different pHs and was used under photolytical conditions in aqueous medium for the reduction of 1,2-diols to alcohols. The conversion steps of 1,2-cyclopentanediol to cyclopentanol via cyclopentanone were analyzed, and it was proven that the reaction proceeds via a dual catalytic/radical chain mechanism. This approach was successfully adapted to the reduction of a variety of carbonyl compounds using H2S at pH 9 in water. This work opens up the field of environmental friendly synthetic processes using the pH-driven modulation of reactivity of this simple reagent in water.
Preparation method of D-borneol
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Paragraph 0032; 0033; 0037; 0042; 0046, (2018/11/22)
The invention relates to a preparation method of D-borneol. The method comprises the following steps: ensuring that natural camphor is reacted for 1 to 8 hours at 0 to 40 DEG C under the existence ofan organic solvent and a chiral reagent (R)-BINAP-H serving as catalysts, and ensuring that the optimized ratio of the organic solvent to the chiral reagent (R)-BINAP-H to camphor is (10-30ml): (20-50mmol): 18mmol.
An efficient FeCl3-mediated approach for reduction of ketones through N-heterocyclic carbene boranes
Wang, Ming-Hui,Chen, Ling-Yan
supporting information, p. 732 - 735 (2017/03/31)
An efficient FeCl3-mediated approach for reduction of ketones by NHC-BH3 has been developed. A series of ketones were smoothly converted to the corresponding alcohols in good to excellent yields through NHC-BH3 reductive process.
