- Preparation method of (R)-(-)-massoialactone
-
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.
- -
-
Paragraph 0055-0058; 0073-0075
(2019/12/25)
-
- Asymmetric Synthesis of α,β-Unsaturated δ-Lactones through Copper(I)-Catalyzed Direct Vinylogous Aldol Reaction
-
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.
- Zhang, Hai-Jun,Yin, Liang
-
p. 12270 - 12279
(2018/09/25)
-
- Trimethylphosphine-Promoted Alcoholysis of α,β-Unsaturated Imides and α,β-Unsaturated Esters
-
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.
- Sato, Haruka,Hosokawa, Seijiro
-
p. 1343 - 1349
(2018/01/27)
-
- Asymmetric Synthesis of Borylalkanes via Copper-Catalyzed Enantioselective Hydroallylation
-
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.
- Han, Jung Tae,Jang, Won Jun,Kim, Namhyeon,Yun, Jaesook
-
supporting information
p. 15146 - 15149
(2016/12/06)
-
- PPARS AGONIST ACTIVITY ENHANCING DRUG
-
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).
- -
-
Paragraph 0042-0043
(2015/03/03)
-
- Enantiomerically pure allylboronic esters as versatile reagents in the enantioselective synthesis of dihydro-α-pyrone-containing natural products
-
A short and efficient enantio- and diastereoselective synthesis of different representatives from the class of dihydro-α-pyrone natural products, including both enantiomers of goniothalamin, massoia lactone, parasorbic acid, and some derivatives is presented. It is based on the application of enantiopure α-chiral allylboronic esters in allyl additions. Georg Thieme Verlag Stuttgart New York.
- Bartlett, Sean,Boese, Dietrich,Ghori, Daniel,Mechsner, Bastian,Pietruszka, Joerg
-
p. 1106 - 1114
(2013/05/21)
-
- Asymmetric synthesis of (+)-(S)-massoia lactone, pheromone of idea leuconoe. formal total synthesis of valilactone and lachnelluloic acid
-
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.
- Mineeva
-
p. 1647 - 1654
(2014/02/14)
-
- Versatile approach for the asymmetric synthesis of (R)- and (S)-massoialactones
-
A general synthetic approach to both enantiomers, (R)- and (S)-massoialactones, has been devised from commercially available (S)-butane-1,2,4-triol. Copyright Taylor & Francis Group, LLC.
- Sabitha, Gowravaram,Gopal,Yadav
-
p. 1495 - 1502
(2008/02/02)
-
- A practical enantioselective synthesis of massoialactone via hydrolytic kinetic resolution
-
An efficient enantioselective synthesis of (R)- and (S)-massoialactone has been achieved. The key steps are the hydrolytic kinetic resolution of a racemic epoxyheptane with (R,R)-(salen)-CoIIIOAc complex and ring-closing metathesis of homoallylic alcohol derived acrylate esters using Grubb's catalyst.
- Gupta, Priti,Naidu, S. Vasudeva,Kumar, Pradeep
-
p. 849 - 851
(2007/10/03)
-
- Diastereoselective dihydroxylation and regioselective deoxygenation of dihydropyranones: A novel protocol for the stereoselective synthesis of C 1-C8 and C15-C21 subunits of (+)-discodermolide
-
Diastereoselective dihydroxylation of dihydropyranones and subsequent regioselective α-deoxygenation provides 1,3-trans-β-hydroxy-6- lactones stereoselectively. This protocol has been applied for the synthesis of C1-C8 and C15-C21 subunits of (+)-discodermolide.
- Ramachandran, P. Veeraraghavan,Prabhudas, Bodhuri,Chandra, J. Subash,Reddy, M. Venkat Ram
-
p. 6294 - 6304
(2007/10/03)
-
- Synthesis of the racemate and both enantiomers of massoilactone
-
A simple and efficient synthesis of (±)-massoilactone (1) as a key substance for the butter and milk flavor was accomplished from n-hexanal in only a few steps. Application of its racemic synthesis enabled natural (R)-(-)-and unnatural (S)-(+)-massoilacto
- Ishikawa, Masashi,Amaike, Masayasu,Itoh, Masamichi,Warita, Yasuhiro,Kitahara, Takeshi
-
p. 2210 - 2214
(2007/10/03)
-
- Diastereoselective reactions of a homoenolate generated from (S)-N-(1-phenylethyl)-3-(trimethylsilyl) propanamide: Enantioselective synthesis of (+)-massoialactone
-
Alkylation of the homoenolate generated from (S)-N-(1-phenylethyl)-3-(trimethylsilyl)propanamide gave the corresponding products with good diastereoselectivity. Starting with one of the alkylated products, enantioselective synthesis of (+)-massoialactone
- Sadayori, Naoko,Kawatoh, Asako,Sakurazawa, Ryoko,Utsumi, Tomoko,Inagaki, Miharu,Asaoka, Morio
-
p. 191 - 202
(2007/10/03)
-
- Optical resolution of fragrant lactones
-
Optical resolution of six chiral fragrant lactones (δ-jasmine lactone, massoia lactone, tuberolactone, pentynyllactone, δ-decalactone, and γ- nonalactone) was investigated by means of either the diastereomeric salt formation method or the diastereomeric amide formation method. Using these procedures, we obtained each enantiomer from five of the six lactones, except for massoia lactone. All five lactones were obtained in a good yield and with high optical purity. Sensoric characteristics on both enantiomers and racemic modification of four lactones are given.
- Nohira, Hiroyuki,Mizuguchi, Keiko,Murata, Toru,Yazaki, Yuko,Kanazawa, Miho,Aoki, Yoshio,Nohira, Misako
-
p. 1359 - 1370
(2007/10/03)
-
- Asymmetric synthesis of (S)-Massoialactone
-
An asymmetric synthesis of (S)-(+)-Massoialactone is described using the Sharpless asymmetric dihydroxylation and the regiospecific nucleophilic opening of a cyclic sulfate as key steps.
- Pais, Godwin C.G.,Fernandes, Rodney A.,Kumar, Pradeep
-
p. 13445 - 13450
(2007/10/03)
-
- Enzyme Assisted Synthesis of Enantiomerically Pure δ-Lactones
-
Both enantiomers series of a wide variety of optically pure 6-alkylated δ-lactones - saturated as well as unsaturated - were prepared via an enzyme mediated route.The key reaction step is the nucleophilic ring opening of enantiomerically pure alkyl-oxiranes, accessible via the corresponding β-hydroxythioesters which can be obtained enantiomerically pure via enzyme catalyzed kinetic resolutions.
- Haase, Bernhard,Schneider, Manfred P.
-
p. 1017 - 1026
(2007/10/02)
-
- A CONVENIENT SYNTHESIS OF HOMOCHIRAL δ-ALKYLATED α,β-UNSATURATED δ-LACTONES
-
The tert-butyl propiolate ion serves as a convenient and efficient nucleophile in boron trifluoride-catalyzed openings of homochiral, mono-substituted epoxides.The resulting tert-butyl 5-hydroxy-2-alkynoates are converted into the title compounds upon semihydrogenation followed by acid hydrolysis.Specific examples include the synthesis of parasorbic acid and massoilactone, two naturally derived lactones of the present type.The scope of the synthetic protocol is discussed.
- Hoeyer, Thomas,Kjaer, Anders,Lykkesfeldt, Jens
-
p. 1042 - 1051
(2007/10/02)
-
- SECONDARY METABOLITES BY CHEMICAL SCREENING - 13. ENANTIOSELECTIVE SYNTHESIS OF δ-LACTONES FROM STREPTENOL A, A CHIRAL BUILDING BLOCK FROM STREPTOMYCES
-
The enantioselective synthesis of all four stereoisomers of the secondary metabolite 3-hydroxy-5-decanolide (4a) from Cephalosporium recifei and both enatiomers of massoialactone (5a) by starting from one chiral building block, streptenol A (1a), a secondary metabolite from Streptomyces sp., is described.The key steps of the reaction sequence involve diastereoselective reduction of 1a to syn- or anti-triol 2a and 2b and the regioselective oxidation of the primary hydroxyl group.This reaction furnishes in one step the δ-lactones 3a and 3b and requires no protecting group.
- Romeyke, Yvonne,Keller, Martin,Kluge, Heinz,Grabley, Susanne,Hammann, Peter
-
p. 3335 - 3346
(2007/10/02)
-
- Enantiomerically Pure Lactones. 3. Synthesis of and Stereospecific Conjugate Additions to α,β-Unsaturated Lactones
-
A general synthetic approach to both enantiomers of α,β-unsaturated lactones of general formula 1 has been devised, the first synthesis of the naturally occuring antipode of massoilactone (1b) exemplifying the approach.Interestingly, the specific rotation of massoilactone (and its enantiomer) is higher than that of the natural material isolated from formicine ants.A key step in the sequence involves chromatographic separation of rationally selected diastereomeric derivatives of racemic intermediates. Compounding the utility of an approach to optically active, type 1 lactones is the observation that conjugate additions of organometallic reagents to such lactones proceed with a high degree of stereospecificity, affording lactones of general formula 2. The conformational behavior of lactone 1a is considered as is the solvation of δ-lactones by fluoroalcoholic chiral solvating agents such as 2,2,2-trifluoro-1-(9-anthryl)ethanol (8).
- Pirkle, William H.,Adams, Paul E.
-
p. 4117 - 4121
(2007/10/02)
-