Total Synthesis of (R)-(−)-β-Cuparenone

Abstract

(R)-(?)-β-Cuparenone has been synthesized from (S)-(+)-acid-2 obtained via resolution of the racemic acid. Two of the noteworthy steps are (a) repeated methylation of ester (+)-8 with LDA/MeI to furnish (+)-10 and (b) the reaction of 12, having two neopentyl units with NaCN.     

Chiral Synthesis of the Key Intermediate of Diterpenoids

(-)-Methyl(4R,5SloR)-l4-methoxyPodocmpa-8,ll,l3-triene-l9-oate(I)isthekeyintermediateforsynthesesofditerpenoidssuchaskaurenoicacid(3),kaur-l6-en-l9-ol(4),monoginol(5)('),aswellasC,,-diterpenealkaloidssuchasveachine(6),garryine(7)andatisine(8)(=).TheracemicsynthesisofthisintermediatewasdonebyK.Morietar'),butthechiralsynthesishasnotbeenreported.Herewepresentthechiralsynthesisofthiskeyintermediatefrom(R)-(+)-2-methyl-2-(2'-nitrovinyl)-5-vaierolactone(2).2wassynthesizedaccordingtoliterattirmeth…     

Design, Synthesis of Chiral Ketone and Application in Asymmetric Epoxidation

A class of chiral ketone was synthesized for asymmetric epoxidation. High ee values have been obtained for a number of cis olefin and trans olefin. The epoxidation was stereospecific with no isomerizatiom observed in the epoxidation of acyclic system. Encourageingly high ee value has also been obtained for a number of terminal olefins. Mechanistic studies show that electronic interactions play an important role in the stereodifferentiation. O O O O O O NBoc O O t-BuO2CH2CN O O O …     

Synthesis of a New Aryl Ether Ketone Polymer

SemicrystallinearyletherketonepolymerssuchasPEEKbelongtoaclassofmaterialsknownasengineeringthermoplastics.PEEKexhibitsarelativelyhighdegreeofcrystallinityandameltingpoint(T.)of335"C.Ontheotherhand,PEEKsuffersfrompoorcreepbehavioraboveitsrelativelylowglasstransitiontemperature(T,)of143"C.Therefore,thesynthesisofnewvariantsisthefocusofmuchresearchl'2.Thesenewvariantsareusuallysemicrystallineinnatureandexhibithighmeltingpoints.Thisresultsinprocessingdifficulties,whichhascreatedaneedforpoly…     

Total Synthesis of (-)-α-Pinguisene

In previous work from our laboratory, we demonstrated that α-carbonyl radical cyclization reactions can serve efficiently as key steps in total synthesis of natural products.1 In this presentation,we report the total synthesis of (-)-α-pinguisene from enone 1 via α-carbonyl radical cyclization.     

Chiral Synthesis of (S)-(+)-γ-Hydroxymethyl-γ-Butyrolactone

S-(+)-γ-hydroxymethyl-gM-butyrolactone has been synthesized from D-ribonolactone as chiral template.     

Synthesis and Structure of a Dinuclear Copper(Ⅱ)-ditetrazolate Involving in situ Ligand Synthesis

The hydrothermal reaction of 1,2-dicyanobenzene with NaN3 in the presence of CuCl2, 2,2′-bipyridine and H2O affords a novel dinuclear copper(II)-ditetrazolate, [Cu(bpy)- (pdtz)]2 (Hpdtz = 5,5′-1,2-phenylene-ditetrazole, bpy = 2,2′-bipyridine). The pdtz ligand is generated in situ through Sharpless 2+3 cycloaddition reaction. Its crystal structure was deter- mined by single-crystal X-ray diffraction method. The crystal crystallizes in the monoclinic system, space group P21/n with a = 8.2096(16), b = 18.580(4), c = 11.838(2) , β = 103.12(3)o, V = 1758.5(6) 3, Z = 2, Mr = 863.83, Dc = 1.631 g/cm3, F(000) = 876 and μ = 1.272 mm-1. In this novel dinuclear structure, the pdtz ligand adopts a peculiar μ2-η1,η2 coordination mode.     

Synthesis of R(−)-3-Benzyl-5(Methoxycarbonyl-Methylthiomethyl)-Hydantoin,A Potential Chiral Intermediate for (+) Biotin

Abstract

Simple and highly efficient synthesis of R(?)-3-benzyl-5 (methoxycarbonylmethylthiomethyl)-hydantoin (7a) from L(+) Cystine (1) is described.     

Synthesis of a Novel Chiral Trihydroxamic Acid Containing L-Pro-L-Ala-L-Ala-β-(HO)Ala-OMe Unit

Iron is indispensable for almost all life forms1. Under iron-deficient environments, microorganisms secrete siderophores to chelate ferric ions and then, transport ferric ions into cells by specific receptor recognitions2,3. Siderophores have many clinica…     

Synthesis of (4R)-α-Terpineol

Thesynthesisofopticallyactivecompoundsisanimportantissueinmodemorgan-icchendstry-7-Terpineol,anaturalproductisolatedfrompetitgrainoil,longleafpineoi1andcaeputoill'J,hasbeenasynthetictargetduringthecourseofourstudiesontheasymmetriccatalisedDiels-AlderreactionlvInthispaper,l-phenylsulfOnyl-3-buten-2-one(l)wasusedasthesulfOnyl-functionalizedche1atingenoneforthesynthesischiral2-Terpineol(5)byaasymmetriccata1isedDiels-Alderreaction.TherouteforthesynthesisofopticallyaCtivea-Terpineo1(5)isshownin…     

Asymmetric Synthesis XIII: The Stereocontrolled Synthesis of (R)—α—Amino Acids via a Double Chiral Induction

The stereocontrolled synthesis of (R)—α—amino acids via a double chiral induction in alkylation of the ketimine derived from (+)—camphor and (+)—menthyl glycinate which is a chiral match pair has been studied. (R)—α—amino acids wih high optical purity 80–90% are obtained after hydrolysis of the alkylated products. We find that the chiral match which is the symergistic effect in a double chiral induction is very important to abtain the higher diastereoselectivity for the stereocontrolled synthesis.     

Synthesis and Crystal Structure of a Chiral Manganese(Ⅲ) Schiff Base Complex

A chiral salency complex,[Mn(Salency)(H2O)2](PF6)·2H2O 1(Salency =(R,R)-N,N'-bis(salicylidene)-1,2-cyclohexanediamine),has been prepared by the reaction of Mn(CH3COO)3·2H2O with Salency and NH4PF6,and was established by X-ray diffraction techniques.The complex crystallizes in triclinic,space group P1 with a=9.299(8),b=10.012(8),c=13.461(11),α=92.037(15),β=92.974(12),γ=93.530(18)°,V=1248.3(18)3,C20H28F6MnN2O6P,Mr = 592.35,Z=2,Dc=1.038 g/cm3,F(000)=608,μ=0.676 mm-1,the final R=0.0651 and wR=0.1880 for 5260 observed reflections with I 2σ(I).     

The Synthesis of a γ-Keto-α-amino Acid,a Key Intermediate in the Synthesis of Monatin,a New Natural Sweetener

An efficient method was developed for the synthesis of the ketoamino acid 2, a key intermediate in the synthesis of the novel sweet compound, monatin 1. Preparation of 2 entails coupling of a suitably protected indole acetate anion to an aspartic acid derivative.     

Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid

(E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.     

Synthesis of Novel Cyclic Aryl Ether Thioether Ketone (Sulfone) Oligomers

Thering-openingpolymerization(ROP)reactionplaysanimportantroIeinproductionofhigh-performancethermoplastics'.ThecyclicoligomersofferauniquecombinationoflowmeltviscosityandthecapabilityofachievingveryhighmolecuIarweightinashortreactiontimewithoutthereleaseofvolatilebyproductsandROPhasbeenanactivesubjectofindustrialandacademicresearch.TheROPsofmanycyclicoligomershavebeenachievedviaanionicpolymerizationinthepresenceofthenucleophilicinitiatorsuchascaesiumfluorideandalkaliphenoxides',butusingthe…     

Total Synthesis of (±)-Epiisocomenes VIA Hydrogenation of “Chatterjee's Ketone”

Dienic acid 5 was transformed into tricyclic ketone 6 in four steps using the cyclopentene annulation of dienic diazoketones. Hydrogenation of 6 under several conditions yielded ketone 7a which was further transformed into β-epiisocomene 4 and epiisocomene 3, contrary to the results previously reported by Samir Chatterjee.     

Synthesis of a New Chiral Cyclicβ-Amino Alcohol

The enantioselective chiral l,3,2-oxazaborolidine-catalyzed reduction of prochiralketones by borane has been intensively investigated'-'. Most oxazaborolidine catalystshave been prepared from chiral D-amino alcohols. In our previous study on the catalyststructure-enantioselectivity relationships, we prepared (R)-2-amino-1,l-diphenyl-3~(2naphthyl)-l-propanol I which proved to be a good precursor of chiral catalyst for theenantioselective borane reduction of prochiral ketones4-9. This let'ter d…     

A Novel Synthesis of (-)-10-epi-α-Cyperone

The eudesmane derivative, (-)-10-epi-α-cyperone 1, is widely used as a chiral starting material for the synthesis of other fused-ring sesquiterpenes1. The first synthetic work was reported by Howe and co-workers via condensation of (+)-dihydrocarvone 2 with 1-diethylaminopentan-3-one methiodide in 32% yield2. Previously, our group reported the synthesis of compound 1 by treating ketone 2 with ethyl vinyl ketone (EVK) directly under different conditions1a, but the yields were not satisfacto…