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Low Enantioselectivities (low + enantioselectivity)

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Chemistry	100%

Selected Abstracts

Better Performance of Monodentate P -Stereogenic Phosphanes Compared to Bidentate Analogues in Pd-Catalyzed Asymmetric Allylic Alkylations

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2010
Arnald Grabulosa
Abstract The cationic allylpalladium complexes 3a,3f, 4a, 4e, 5e of type [Pd(,3 -2-Me-C3H4)P2]PF6 were synthesized using a group of monodentate P -stereogenic phosphanes, P=PPhRR, (a,f) and diphosphanes (PhRPCH2)2 (1a, 1e) or PhRPCH2Si(Me)2CH2PPhR (2e). The analogous cationic complexes with the disubstituted allyl group (,3 -1,3-Ph2 -C3H3) and monodentate phosphanes were not isolated as stable solids; only [PdCl(,3 -1,3-Ph2 -C3H3)P] (6a, 6d) were obtained. Palladium allyl complexes were screened as precatalysts in the allylic substitution of rac -3-acetoxy-1,3-diphenyl-1-propene (I) and (E)-3-acetoxy-1-phenyl-1-propene (III) with dimethyl malonate as the nucleophile. The various catalytic precursors showed a wide range of activity and selectivity. The bismonodentate phosphane complexes 3 are more active than the bidentate analogues. With regard to the regioselectivity, precursors containing monodentate phosphanes favour the formation of the linear product in the allylic substitution of cinnamyl acetate (III) compared with those containing bidentate phosphanes. With substrate I, compounds with the diphosphanes 1a and 1e, containing a five-membered chelate ring, gave low enantioselectivities (less than 10,% ee), but those with the diphosphane 2e, forming a six-membered chelate ring or with two monodentate phosphanes, afforded products with moderate enantioselectivity under standard conditions (ee up to 74,%). The results show that the performance of precursors containing monodentate phosphanes was superior to those containing bidentate ligands in both activity and selectivity. [source]

Aqueous Asymmetric Mukaiyama Aldol Reaction Catalyzed by Chiral Gallium Lewis Acid with Trost-Type Semi-Crown Ligands

ADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2005
Hui-Jing Li
Abstract The combination of Ga(OTf)3 with chiral semi-crown ligands (1a,e) generates highly effective chiral gallium Lewis acid catalysts for aqueous asymmetric aldol reactions of aromatic silyl enol ethers with aldehydes. A ligand-acceleration effect was observed. Water is essential for obtaining high diastereoselectivity and enantioselectivity. The p -phenyl substituent in aromatic silyl enol ether (2,h) plays an important role and increases the enantioselectivity up to 95% ee. Although aliphatic silyl enol ethers provided low enantioselectivities and silylketene acetal is easily hydrolyzed in aqueous alcohol, the aldol reactions of silylketene thioacetal (12) with aldehydes in the presence of gallium-Lewis acid catalysts give the ,-hydroxy thioester with reasonable yields and high diastereo- (up to 99,:,1) and enantioselectivities (up to 96% ee). [source]

Stereoselectivity of Pseudomonas cepacia lipase toward secondary alcohols: A quantitative model

PROTEIN SCIENCE, Issue 6 2000
Tanja Schulz
Abstract The lipase from Pseudomonas cepacia represents a widely applied catalyst for highly enantioselective resolution of chiral secondary alcohols. While its stereopreference is determined predominantly by the substrate structure, stereoselectivity depends on atomic details of interactions between substrate and lipase. Thirty secondary alcohols with published E values using P. cepacia lipase in hydrolysis or esterification reactions were selected, and models of their octanoic acid esters were docked to the open conformation of P. cepacia lipase. The two enantiomers of 27 substrates bound preferentially in either of two binding modes: the fast-reacting enantiomer in a productive mode and the slow-reacting enantiomer in a nonproductive mode. Nonproductive mode of fast-reacting enantiomers was prohibited by repulsive interactions. For the slow-reacting enantiomers in the productive binding mode, the substrate pushes the active site histidine away from its proper orientation, and the distance d(HN, , Oalc) between the histidine side chain and the alcohol oxygen increases. d(HN, , Oalc) was correlated to experimentally observed enantioselectivity: in substrates for which P. cepacia lipase has high enantioselectivity (E > 100), d(HN, , Oalc) is>2.2 Å for slow-reacting enantiomers, thus preventing efficient catalysis of this enantiomer. In substrates of low enantioselectivity (E < 20), the distance d(HN, , Oalc) is less than 2.0 Å, and slow- and fast-reacting enantiomers are catalyzed at similar rates. For substrates of medium enantioselectivity (20 < E< 100), d(HN, , Oalc) is around 2.1 Å. This simple model can be applied to predict enantioselectivity of P. cepacia lipase toward a broad range of secondary alcohols. [source]

Asymmetric Sulfonium Ylide Mediated Cyclopropanation: Stereocontrolled Synthesis of (+)-LY354740

CHEMISTRY - A EUROPEAN JOURNAL, Issue 2 2006
Varinder K. Aggarwal Prof.
Abstract The reaction of ester-stabilized sulfonium ylides with cyclopentenone to give (+)- 5 ((1S,5R,6S)-ethyl 2-oxobicyclo[3.1.0]hexane-6-carboxylate), an important precursor to the pharmacologically important compound (+)-LY354740, has been studied using chiral sulfides operating in both catalytic (sulfide, Cu(acac)2, ethyl diazoacetate, 60,°C) and stoichiometric modes (sulfonium salt, base, room temperature). It was found that the reaction conditions employed had a major influence over both diastereo- and enantioselectivity. Under catalytic conditions, good enantioselectivity with low diastereoselectivity was observed, but under stoichiometric conditions low enantioselectivity with high diastereoselectivity was observed. When the stoichiometric reactions were conducted at high dilution, diastereoselectivity was reduced. This indicated that base-mediated betaine equilibration was occurring (which is slow relative to ring closure at high dilution). Based on this model, conditions for achieving high enantioselectivity were established as follows: use of a preformed ylide, absence of base, hindered ester (to reduce ylide-mediated betaine equilibration), and low concentration. Under these conditions high enantioselectivity (95,% ee) was achieved, albeit with low diastereocontrol. Our model for selectivity has been applied to other sulfonium ylide mediated cyclopropanation reactions and successfully accounts for the diastereoselectivity observed in all such reported reactions to date. [source]