Synthesis of Conjugated Trienes and Related Oxidation Products of α-Farnesene

1994 ◽  
Vol 47 (11) ◽  
pp. 1979 ◽  
Author(s):  
MA Brimble ◽  
DD Rowan ◽  
JA Spicer
Keyword(s):  
Ring Opening ◽  
Room Temperature ◽  
Oxidation Products ◽  
Epoxide Ring ◽  
Epoxide Ring Opening ◽  
Superficial Scald ◽  
Conjugated Trienes ◽  
Conjugated Triene ◽  
Cyclic Peroxide

The synthesis of conjugated trienes and related oxidation products of α- farnesene (1), principally from the epoxides of α- farnesene (1), is reported. Base-promoted ring opening of 6,7-epoxide (4) by KOBut/LiNPri2 affords the conjugated triene (2), whilst the 3,4-epoxide (5) affords trienol (7). In contrast, 10,11-epoxide (6) fails to undergo epoxide ring opening; it rearranges to the conjugated triene epoxide (8). Base-promoted ring opening of bisepoxide (9) afforded trienol epoxide (11) at -30°C, whilst cyclization to tetrahydrofurans (10a,b) occurred at room temperature. Photosensitized oxidation of 10,11-epoxide (6) followed by in situ treatment with acid gave the cyclic peroxide (3) and on reduction triol (12). Bisallylic alcohol (13) was prepared by alkylation of 3-methylsulfolene with geranial. Trienes (2) and (3) have been isolated previously as autoxidation products of α- farnesene (1) and are implicated as the causal agents of superficial scald of stored apples.

scholarly journals SYNTHESIS, PREPARATIVE SEPARATION OF STRUCTURE ISOMERS AND PROPERTIES OF 2-(2-(DIALKYLAMINO)ETHYLAMINO)ETHANOLS OF ARYLALIPHATIC SERIES

2017 ◽  
Vol 12 (1) ◽  
pp. 57-63
Author(s):  
D. Q. Hoang ◽  
E. Ya. Borisova ◽  
N. Yu. Borisova ◽  
A. V. Krylov ◽  
N. A. Danilkin ◽  
...  
Keyword(s):  
Ring Opening ◽  
Room Temperature ◽  
Mixed Solvent ◽  
Sodium Hydroxide Solution ◽  
Styrene Oxide ◽  
Aqueous Sodium Hydroxide ◽  
Epoxide Ring ◽  
1H And 13C Nmr ◽  
Epoxide Ring Opening ◽  
Ft Ir

A method for the synthesis of 2-(2-(dialkylamino)ethylamino)ethanols based on the epoxide ring opening in styrene oxide by N,N-disubstituted ethylenediamines was developed. It is shown that the opening of the oxirane ring by diamines in 2-propanol at room temperature occurs mainly according to the Krasusky rule at the bond between the oxygen atom and the less substituted carbon atom. A mixture of two products with the predominance of the secondary diamino alcohol up to 82% was obtained. It was found that the separation of the products by distillation or recrystallization does not allow obtaining pure isomers. The mixture of isomers was converted into dihydrochlorides by dry HCl in dioxane and diethyl ether. Pure 2-(2-(dialkylamino)ethylamino)-1-phenylethanols and 2-(2-(dialkylamino)ethylamino)-2-phenylethanols were separated by the first fractional recrystallization of a mixture of diaminoalcohol dihydrochlorides from a mixed solvent followed by alkalization of the products with an aqueous sodium hydroxide solution. The diamino alcohols were characterized by FT-IR, 1H- and 13C-NMR and HRMS-ESI.

scholarly journals Synthesis of Optically Active Maresin 2 and Maresin 2n-3 DPA

Synlett ◽  
2020 ◽  
Author(s):  
Narihito Ogawa ◽  
Takahito Amano ◽  
Yuichi Kobayashi
Keyword(s):  
Ring Opening ◽  
Optically Active ◽  
Epoxide Ring ◽  
Sonogashira Coupling ◽  
Epoxide Ring Opening ◽  
Lipid Metabolites ◽  
Swern Oxidation ◽  
Stereoselective Syntheses

AbstractMaresins are among the most potent antiinflammatory lipid metabolites. We report stereoselective syntheses of maresin 2 and maresin 2n-3 DPA. The anti-diol was constructed through epoxide ring opening of an optically active β,γ-epoxy aldehyde, synthesized in situ by Swern oxidation of the corresponding alcohol. Finally, the target compounds were synthesized through a Sonogashira coupling of a C9–C22 iodide and methyl (Z)-oct-4-en-7-ynoate or methyl oct-7-ynoate, respectively.

A protecting group free and scalable approach towards total synthesis of (−)-venlafaxine

RSC Advances ◽  
2014 ◽  
Vol 4 (28) ◽  
pp. 14468-14470 ◽  
Author(s):  
Subhash P. Chavan ◽  
Kailash P. Pawar ◽  
Sumanta Garai
Keyword(s):  
Total Synthesis ◽  
Ring Opening ◽  
Epoxide Ring ◽  
Protecting Group ◽  
Asymmetric Total Synthesis ◽  
Epoxide Ring Opening ◽  
Key Steps

A protecting group free asymmetric total synthesis of (−)-venlafaxine is reported. The strategy employs Sharpless epoxidation and regio-selective epoxide ring opening by an in situ generated Gilman reagent as key steps. This paper reports a 53% overall yield in 6 steps for total synthesis of (−)-venlafaxine.

scholarly journals (29) MCP Treatment Makes Delayed Application of Ethoxyquin Effective in Control of Superficial Scald of `d'Anjou' Pears

HortScience ◽  
2005 ◽  
Vol 40 (4) ◽  
pp. 1004A-1004
Author(s):  
Jinhe Bai
Keyword(s):  
Ethylene Production ◽  
Room Temperature ◽  
Oxidation Products ◽  
Mass Treatment ◽  
Fruit Peel ◽  
Superficial Scald ◽  
Conjugated Trienes

Superficial scald of `d'Anjou' pears usually develops after storage of 2 months or longer. MCP application controls scald; however, fruit lose their ripening capacity if the dosage is >30 ppb, but lower dosages cannot control scald substantially. In this study, fruit treated with or without 25 ppb MCP within 2 d after harvest were stored at –1 °C for up to 5 months. After 1, 7, 30, or 70 d of storage, part of the fruit were pulled from storage and treated with 1000 ppm ethoxyquin line spray and immediately returned to the storage, left untreated as non-ethoxyquin control. Incidence of superficial scald along with the concentrations of α-farnesene and conjugated trienes (CTs), and the ripening capacity of fruit were investigated after 3, 4, and 5 months storage. All fruit ripened properly within 7 d of conditioning at room temperature regardless of treatments. Both of MCP or ethoxyquin-1d (ethoxyquin was applied after 1 day storage at –1 °C) alone controlled scald for only 3 months; however, MCP + ethoxyquin controlled scald for 5 months, whenever ethoxyquin was applied between 1 to 70 d after storage. Thus, with 25 ppb MCP treatment, which is simple, with rapid and mass treatment available, a delayed application (up to 70 d) of ethoxyquin becomes effective to control scald. Furthermore, the later application of ethoxyquin within 70 d after MCP treatment, the less incidence of scald was observed. Scald is caused by the CTs oxidation products of α-farnesene. MCP and ethoxyquin inhibited accumulation of CTs of fruit peel by different mechanisms. MCP inhibited the production by influencing ethylene production through control of α-farnesene synthesis; however, ethoxyquin worked by inhibiting the oxidation of α-farnesene to the CTs.

Bimetallic Radical Redox-Relay Catalysis for the Isomerization of Epoxides to Allylic Alcohols

2019 ◽  
Author(s):  
Ke-Yin Ye ◽  
Terry McCallum ◽  
Song Lin
Keyword(s):  
Ring Opening ◽  
High Reactivity ◽  
Hydrogen Atom Transfer ◽  
Organic Radicals ◽  
Epoxide Ring ◽  
Allylic Alcohols ◽  
Epoxide Ring Opening ◽  
Bond Forming ◽  
Co Catalysts ◽  
The Rich

Organic radicals are generally short-lived intermediates with exceptionally high reactivity. Strategically, achieving synthetically useful transformations mediated by organic radicals requires both efficient initiation and selective termination events. Here, we report a new catalytic strategy, namely bimetallic radical redox-relay, in the regio- and stereoselective rearrangement of epoxides to allylic alcohols. This approach exploits the rich redox chemistry of Ti and Co complexes and merges reductive epoxide ring opening (initiation) with hydrogen atom transfer (termination). Critically, upon effecting key bond-forming and -breaking events, Ti and Co catalysts undergo proton-transfer/electron-transfer with one another to achieve turnover, thus constituting a truly synergistic dual catalytic system.<br>

Construction the A-B bicyclic ring structure of Stemocurtisisne

2020 ◽  
Vol 17 ◽  
Author(s):  
Duc Dau Xuan
Keyword(s):  
Glutamic Acid ◽  
Natural Product ◽  
Mannich Reaction ◽  
Boronic Acid ◽  
Ring Opening ◽  
Ring Structure ◽  
Starting Material ◽  
Epoxide Ring ◽  
Epoxide Ring Opening

: The synthesis of the A-B bicyclic ring structure 3 of the natural product Stemocurtisine is described. The synthesis was accomplished in seven synthetic steps from commercially available L-glutamic acid. The key step involved a borono-Mannich reaction between the hemiaminal 6 and trans-β-styryl boronic acid and trans-β-styrylpotassiumtrifluoroborate to prepare the cis diene 4. Attempts to prepare the A-B-C ring compound 2 via intramolecular epoxide ring opening followed by rearangement under different basic conditions were unsuccessful. Only unreactive starting material was recovered.

scholarly journals Thermal and Electrochemical Properties of Solid Polymer Electrolytes Prepared via Lithium Salt-Catalyzed Epoxide Ring Opening Polymerization

2021 ◽  
Vol 11 (4) ◽  
pp. 1561
Author(s):  
Gabrielle Foran ◽  
Nina Verdier ◽  
David Lepage ◽  
Arnaud Prébé ◽  
David Aymé-Perrot ◽  
...  
Keyword(s):  
Electrochemical Properties ◽  
Polymer Electrolytes ◽  
Ring Opening ◽  
Lithium Salt ◽  
Ring Opening Polymerization ◽  
Solid Polymer Electrolytes ◽  
Solid Polymer ◽  
Polymerization Reaction ◽  
Epoxide Ring ◽  
Epoxide Ring Opening

Solid polymer electrolytes have been widely proposed for use in all solid-state lithium batteries. Advantages of polymer electrolytes over liquid and ceramic electrolytes include their flexibility, tunability and easy processability. An additional benefit of using some types of polymers for electrolytes is that they can be processed without the use of solvents. An example of polymers that are compatible with solvent-free processing is epoxide-containing precursors that can form films via the lithium salt-catalyzed epoxide ring opening polymerization reaction. Many polymers with epoxide functional groups are liquid under ambient conditions and can be used to directly dissolve lithium salts, allowing the reaction to be performed in a single reaction vessel under mild conditions. The existence of a variety of epoxide-containing polymers opens the possibility for significant customization of the resultant films. This review discusses several varieties of epoxide-based polymer electrolytes (polyethylene, silicone-based, amine and plasticizer-containing) and to compare them based on their thermal and electrochemical properties.

ChemInform Abstract: NEIGHBORING GROUP EFFECTS IN EPOXIDE RING OPENING, CIS-EPOXY-ALCOHOLS

1976 ◽  
Vol 7 (42) ◽  
pp. no-no
Author(s):  
ERWIN GLOTTER ◽  
PNINA KRINSKY ◽  
MIRIAM REJTOE ◽  
MARTIN WEISSENBERG
Keyword(s):  
Ring Opening ◽  
Epoxide Ring ◽  
Neighboring Group ◽  
Epoxide Ring Opening ◽  
Epoxy Alcohols ◽  
Group Effects

An analysis of the factors contributing to the regioselectivity observed in the opening of oxiranes

1980 ◽  
Vol 58 (3) ◽  
pp. 302-306 ◽  
Author(s):  
Margaret M. Kayser ◽  
Peter Morand
Keyword(s):  
Oxygen Atom ◽  
Ring Opening ◽  
Oxirane Ring ◽  
Epoxide Ring ◽  
Acid Base ◽  
Epoxide Ring Opening ◽  
Soft Acid ◽  
Hsab Theory

The regioselectivity of epoxide ring opening can be analyzed in terms of hard–soft acid–base (HSAB) theory. The coordination of the hard acid with the oxygen atom of the oxirane ring produces a "pulling effect" which determines the direction of the ring opening. In the absence of a strong "pulling effect" the "pushing effect" of the approaching base is examined and the consequences of relative softness or hardness of the nucleophile on the regioselectivity of the ring opening are discussed.

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