24587-53-9Relevant academic research and scientific papers
1-Octen-3-ol Is Formed from Its Glycoside during Processing of Soybean [ Glycine max (L.) Merr.] Seeds
Matsui, Kenji,Takemoto, Hiroyuki,Koeduka, Takao,Ohnishi, Toshiyuki
, p. 7409 - 7416 (2018)
Soaking and maceration of dry soybean seeds induce the formation of aliphatic volatile compounds that impact the flavor properties of food products prepared from soybean. Most aliphatic volatile compounds are formed through oxygenation of unsaturated fatty acids by lipoxygenases; however, lipoxygenases are not responsible for the formation of 1-octen-3-ol. 1-Octen-3-ol in soybean products is in general an off-flavor compound; thus, a procedure to manage its formation is required. In this study, we show that the formation of 1-octen-3-ol after hydration of soybean seed powder is independent of oxygen, suggesting that 1-octen-3-ol is not formed de novo from unsaturated fatty acids but instead from its derivative. When crude methanol extract of soybean seeds was reacted with β-glycosidases, 1-octen-3-ol was rather liberated from its glycoside. We purified the parent glycoside from soybean seeds and confirmed it as (R)-1-octen-3-yl β-primeveroside [(R)-1-octen-3-yl 6-O-β-d-xylopyranosyl-β-d-glucopyranoside]. Green immature soybean fruits (pericarp and seeds) contain a high amount of 1-octen-3-yl β-primeveroside. Its amount decreases after hydration of dry soybean powder. The results indicate that management of 1-octen-3-ol levels in soybean products requires a different strategy than that applied to off-flavor compounds formed de novo.
A stereoselective synthesis of the reported structure of polyporolide
Patil, Pradnya H.,Fernandes, Rodney A.
, p. 49189 - 49194 (2015)
Polyporolide, isolated from a basidiomycete, was assigned a 4-hydroxy-5-(1-hydroxyhexyl)-dihydrofuran-2-one structure with anti-placement of the three contiguous stereocenters. A stereoselective total synthesis of the reported structure of the natural product involving two different routes is presented. A comparison of the spectral data of the synthesized molecule indicates the need for structure revision of natural polyporolide.
A general asymmetric synthesis of (R)-Matsutakeol and flavored analogs
Liu, Jia,Li, Honglian,Zheng, Chao,Lu, Shichao,Guo, Xianru,Yin, Xinming,Na, Risong,Yu, Bin,Wang, Min
, (2017)
An efficient and practical synthetic route toward chiral matsutakeol and analogs was developed by asymmetric addition of terminal alkyne to aldehydes. (R)-matsutakeol and other flavored substances were feasibly synthesized from various alkylaldehydes in high yield (up to 49.5%, in three steps) and excellent enantiomeric excess (up to >99%). The protocols may serve as an alternative asymmetric synthetic method for active small-molecule library of natural fatty acid metabolites and analogs. These chiral allyl alcohols are prepared for food analysis and screening insect attractants.
Modular enantioselective synthesis of 8-aza-prostaglandin E1
Wang, Xiao-Gang,Wang, Ai-E,Hao, Yi,Ruan, Yuan-Ping,Huang, Pei-Qiang
, p. 9488 - 9493 (2013)
We report herein for the first time the enantioselective synthesis of 8-aza-PGE1. The synthesis used the cross olefin metathesis reaction to connect the 5-vinyl-γ-lactam subunit, prepared from (R)-malic acid via the Ley's sulfone-based α-amidalkylation protocol (dr = 6.8:1), with the chiral pre-ω-chain. The latter was synthesized in high enantioselectivity from (E)-2-octenol by the Sharpless asymmetric epoxidation and the titanocene-mediated epoxide opening. This modular approach is quite concise and flexible, and requires only eight steps from commercially available reagents.
Sequential Pd(0)-, Rh(I)-, and Ru(II)-catalyzed reactions in a nine-step synthesis of clinprost
Nagy, Emma E.,Hyatt, I. F. Dempsey,Gettys, Kristen E.,Yeazell, Shawn T.,Frempong Jr., Stephen K.,Croatt, Mitchell P.
, p. 586 - 589 (2013)
A step-economical synthesis of clinprost is reported that concludes with 3 different transition metal-catalyzed reactions: Pd-catalyzed decarboxylation with allylic rearrangement, Rh-catalyzed diene-ene [2+2+1] reaction, and Ru-catalyzed cross-metathesis reaction. The complexity bestowed to the molecule from these reactions converts a readily accessible ester to clinprost without using protecting groups in only 9 total steps.
Concise, scalable and enantioselective total synthesis of prostaglandins
Zhang, Fuhao,Zeng, Jingwen,Gao, Mohan,Wang, Linzhou,Chen, Gen-Qiang,Lu, Yixin,Zhang, Xumu
, p. 692 - 697 (2021/06/01)
Prostaglandins are among the most important natural isolates owing to their broad range of bioactivities and unique structures. However, current methods for the synthesis of prostaglandins suffer from low yields and lengthy steps. Here, we report a practicability-oriented synthetic strategy for the enantioselective and divergent synthesis of prostaglandins. In this approach, the multiply substituted five-membered rings in prostaglandins were constructed via the key enyne cycloisomerization with excellent selectivity (>20:1 d.r., 98% e.e.). The crucial chiral centre on the scaffold of the prostaglandins was installed using the asymmetric hydrogenation method (up to 98% yield and 98% e.e.). From our versatile common intermediates, a series of prostaglandins and related drugs could be produced in two steps, and fluprostenol could be prepared on a 20-gram scale. [Figure not available: see fulltext.]
Pickering-Droplet-Derived MOF Microreactors for Continuous-Flow Biocatalysis with Size Selectivity
Liang, Linfeng,Shi, Hu,Tian, Danping,Wang, Jun-Hao,Xue, Nan,Yang, Hengquan,Zhang, Xiaoming
supporting information, p. 16641 - 16652 (2021/10/20)
Enzymatic microarchitectures with spatially controlled reactivity, engineered molecular sieving ability, favorable interior environment, and industrial productivity show great potential in synthetic protocellular systems and practical biotechnology, but their construction remains a significant challenge. Here, we proposed a Pickering emulsion interface-directed synthesis method to fabricate such a microreactor, in which a robust and defect-free MOF layer was grown around silica emulsifier stabilized droplet surfaces. The compartmentalized interior droplets can provide a biomimetic microenvironment to host free enzymes, while the outer MOF layer secludes active species from the surroundings and endows the microreactor with size-selective permeability. Impressively, the thus-designed enzymatic microreactor exhibited excellent size selectivity and long-term stability, as demonstrated by a 1000 h continuous-flow reaction, while affording completely equal enantioselectivities to the free enzyme counterpart. Moreover, the catalytic efficiency of such enzymatic microreactors was conveniently regulated through engineering of the type or thickness of the outer MOF layer or interior environments for the enzymes, highlighting their superior customized specialties. This study provides new opportunities in designing MOF-based artificial cellular microreactors for practical applications.
Metathesis at an Implausible Site: A Formal Total Synthesis of Rhizoxin D
Karier, Pol,Ungeheuer, Felix,Ahlers, Andreas,Anderl, Felix,Wille, Christian,Fürstner, Alois
supporting information, p. 248 - 253 (2018/12/13)
The new approach to the anticancer agent rhizoxin D described herein does not cohere with the conventional logic of metathesis, according to which macrocycles are best closed at a disubstituted olefinic site; rather, the trisubstituted C11?C12 alkene flanked by an allylic -OH group served as the pivot point for synthesis. This motif was attained in good yield and excellent selectivity by a sequence of alkyne metathesis, trans-hydrostannation and cross coupling. Because the exact same substructure is prominently featured in numerous other natural products, the underpinning strategy, though unusual, might bear more general relevance.
Total synthesis of PGF2α and 6,15-diketo-PGF1α and formal synthesis of 6-keto-PGF1α via three-component coupling
Kim, Taehyeong,Lee, Sung Il,Kim, Sejin,Shim, Su Yong,Ryu, Do Hyun
, (2019/09/17)
The asymmetric total synthesis of PGF2α and 6,15-diketo-PGF1α and formal synthesis of 6-keto-PGF1α from a common key intermediate are described. The key intermediate, which has a chiral cyclopentane backbone possessing suitable functional groups with required stereochemistry for both side chains, was prepared from (R)-4-silyloxy-2-cyclopentenone through a three-component coupling reaction. The Wittig reaction, Nozaki-Hiyama-Kishi (NHK) coupling and cross metathesis completed the synthesis of PGF2α, 6,15-diketo-PGF1α and 6-keto-PGF1α.
Structurally diverse glycoconjugated volatile compounds from Oxytropis falcata Bunge
Wang, Shanshan,Zhang, Xiaojing,Que, Sheng,Liang, Hong,Tu, Pengfei,Zhang, Qingying
, p. 143 - 147 (2018/07/29)
A phytochemical investigation on the whole plant of Oxytropis falcata Bunge yielded 16 glycoconjugated compounds with structurally diverse volatile aglycones but similar sugars. Of these, five were previously undescribed compounds with different volatile aglycones but same glucuronic acid (1 → 2) glucosyl moiety, including three octanol glucuronic acid (1 → 2) glucosides (1–3), one acyclic monoterpenoid glucuronic acid (1 → 2) glucoside (4), and one 4-phenyl-butan-2-ol glucuronic acid (1 → 2) glucoside (5), and 11 were biological related known glucoconjugated volatile compounds (6–16) isolated from genus Oxytropis for the first time. The structures of these compounds were determined by extensive spectroscopic analysis of MS, 1D and 2D NMR data. The absolute configurations of aglycones and sugar residues were assigned via enzymatic hydrolysis and subsequently comparison of the specific rotations. This is the first report of such structurally diverse glycoconjugated volatile compounds from O. falcata, which might be regarded as the precursor of free volatile compounds, and presents scientific evidences for better clarifying the volatile compositions of this medicinal plant and genus Oxytropis.
