54814-64-1Relevant academic research and scientific papers
Asymmetric synthesis of (+)-(S)-massoia lactone, pheromone of idea leuconoe. formal total synthesis of valilactone and lachnelluloic acid
Mineeva
, p. 1647 - 1654 (2013)
Simple and efficient asymmetric synthesis was developed of the cyclic scaffold of (-)-valilactone, an effective inhibitor of the pancreas lipase, applying the Keck allylation in the key stage of building up the carbon skeleton of the target molecule and of the unnatural (S)-isomer of Massoia lactone, lachnelluloic acid, possessing fungicidal properties, and (5R,7S)- 7-hydroxy-5-dodecanolid, pheromone component of the Large Tree Nymph butterfl y Idea leuconoe. Pleiades Publishing, Ltd., 2013.
Allyl-Nickel Catalysis Enables Carbonyl Dehydrogenation and Oxidative Cycloalkenylation of Ketones
Huang, David,Szewczyk, Suzanne M.,Zhang, Pengpeng,Newhouse, Timothy R.
supporting information, p. 5669 - 5674 (2019/04/26)
We herein disclose the first report of a first-row transition metal-catalyzed α,β-dehydrogenation of carbonyl compounds using allyl-nickel catalysis. This development overcomes several limitations of previously reported allyl-palladium-catalyzed oxidation, and is further leveraged for the development of an oxidative cycloalkenylation reaction that provides access to bicycloalkenones with fused, bridged, and spirocyclic ring systems using unactivated ketone and alkene precursors.
Preparation method of (R)-(-)-massoialactone
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Paragraph 0055-0062, (2019/12/25)
The invention discloses a preparation method of (R)-(-)-massoialactone. The preparation method includes the following steps: in a solvent, under the action of a copper salt, an alkali and a ligand, beta,gamma-unsaturated ester and n-hexanal are subjected to a reaction shown in the specification to obtain (R)-(-)-massoalactrone; the copper salt is Cu(CH3CN)4PF6 or the alkali is Barton's Base, alkali metal tert-butanol salt or the ligand is (R,R)-Ph-BPE or (S)-DTBM-SEGPHOS. (R)-(-)-massoialactone can be obtained by one-step reaction with high yield and ee value; compared with other methods in the prior art, the method has many advantages, such as simple route, easy access to raw materials, mild conditions and the like, and has obvious advantages.
Enzyme-mediated enantioselective hydrolysis of 1,2-diol monotosylate derivatives bearing an unsaturated substituent
Matsumoto,Oohana,Hashimoto,Usuda,Shimoda,Ohshima,Suzuki,Togawa
, p. 3981 - 3988 (2018/06/15)
We have succeeded in the easy preparation of optically active 1,2-diol monotosylates bearing an unsaturated substituent via enzymatic hydrolysis. Lipase PS quickly catalyzes the hydrolyses of 2-acetoxybut-3-enyl tosylate, which has a double bond, and 2-acetoxybut-3-ynyl tosylate, which has a triple bond, with excellent enantioselectivity to afford the corresponding optically active compounds. The reaction is also applicable to acetates with a longer chain, which has a double bond at the terminus. To demonstrate the applicability of this method, enantiomerically pure (R)-massoialactone, a natural coconut flavor, has been synthesized from racemic 2-acetoxypent-4-enyl tosylate in several steps. Furthermore, the enzyme can recognize the stereochemistry of olefins, and the (Z)-alkenyl structure is more suitable for the enantioselective hydrolysis than the (E)-isomer.
Rationally Designed Chiral Synthons Enabling Asymmetric Z- and E-Selective Vinylogous Aldol Reactions of Aldehydes
Padarti, Akhil,Han, Hyunsoo
supporting information, p. 1448 - 1452 (2018/03/09)
In a conceptually different approach, highly stereoselective 2-oxonia-Cope rearrangement reactions between rationally designed nonracemic vinylogous aldolation synthons and aldehydes are described to provide δ-hydroxy-α,β-unsaturated esters with excellent
Asymmetric Synthesis of α,β-Unsaturated δ-Lactones through Copper(I)-Catalyzed Direct Vinylogous Aldol Reaction
Zhang, Hai-Jun,Yin, Liang
, p. 12270 - 12279 (2018/09/25)
A simple methodology for the asymmetric synthesis of chiral α,β-unsaturated δ-lactones was achieved by copper(I)-catalyzed direct vinylogous aldol reaction (DVAR) of β,γ-unsaturated esters and various aldehydes, including aromatic aldehydes, heteroaromatic aldehydes, α,β-unsaturated aldehydes, and aliphatic aldehydes. For aromatic and heteroaromatic aldehydes, a one-pot reaction consisting of DVAR, isomerization of the unsaturated carbon-carbon double bond from (E)-form to (Z)-form, and subsequent intramolecular transesterification was required to get the lactones in moderate to high yields with high enantioselectivity. For α,β-unsaturated and aliphatic aldehydes, the DVAR proceeded directly to afford the lactones in moderate yields with high enantioselectivity. In the DVAR, various functional groups were well tolerated. Moreover, the methodology was nicely applicable to the aldehyde group distributed in natural products, derivatives of natural product, and derivatives of drug molecules (atomoxetine and naproxen). The mechanism studies revealed that α-addition was reversible and not favored, which accounted for the excellent regioselectivity in the DVAR. The copper(I)-dienolate species generated through deprotonation was proposed to form an equilibrium with an allylcopper(I) species, which reacted with aldehydes to afford the DVAR products through a catalytic asymmetric allylation of aldehydes. Finally, the robustness of the present reaction was demonstrated by a gram-scale reaction, and the utility of the present methodology was showcased by the formal asymmetric synthesis of ezetimibe and fostriecin.
Trimethylphosphine-Promoted Alcoholysis of α,β-Unsaturated Imides and α,β-Unsaturated Esters
Sato, Haruka,Hosokawa, Seijiro
, p. 1343 - 1349 (2018/01/27)
α,β-Unsaturated imides and α,β-unsaturated esters were found to undergo alcoholysis in the presence of trimethylphosphine. The reaction is initiated by nucleophilic addition of trimethylphosphine to the double bond of the α,β-unsaturated carbonyl compound. Saturated imides also undergo the alcoholysis in the presence of the corresponding α,β-unsaturated imide.
General, Highly Selective Synthesis of 1,3- and 1,4-Difunctionalized Building Blocks by Regiodivergent Epoxide Opening
Funken, Nico,Mühlhaus, Felix,Gans?uer, Andreas
supporting information, p. 12030 - 12034 (2016/11/16)
We describe a regiodivergent epoxide opening (REO) featuring a catalyst-controlled synthesis of enantiomerically and diastereomerically highly enriched or pure syn- and anti- 1,3- and 1,4-difunctionalized building blocks from a common epoxide precursor. The REO is attractive for natural product synthesis and as a branching reaction for diversity-oriented synthesis with epoxides.
Asymmetric Synthesis of Borylalkanes via Copper-Catalyzed Enantioselective Hydroallylation
Han, Jung Tae,Jang, Won Jun,Kim, Namhyeon,Yun, Jaesook
, p. 15146 - 15149 (2016/12/06)
An efficient synthetic method for preparing enantioenriched secondary borylalkanes has been achieved through a copper-catalyzed regio- and enantioselective hydroallylation of alkenyl boronates and boramides employing hydrosilanes and allylic phosphates. In the presence of a copper catalyst with a chiral Walphos ligand, a range of alkenylboron compounds with an aryl, heteroaryl, or alkyl substituent produced secondary homoallylic alkylboron compounds in good yields and with high enantioselectivities up to 99% ee. The utility of the resulting alkylboronates was demonstrated in an efficient synthesis of (S)-massoialactone.
PPARS AGONIST ACTIVITY ENHANCING DRUG
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Paragraph 0018-0019; 0021-0022, (2015/03/03)
According to the present invention, PPARs agonist activity is enhanced in order to improve metabolic syndrome, hyperlipidemia, and diabetes. Provided is a compound having a lactone structure comprising formula (9).
