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Planar Chiral (planar + chiral)
Selected AbstractsSynthesis of Planar Chiral [2.2]Paracyclophane Monophosphine Ligands and Their Application in the Umpolung Allylation of Aldehydes.CHEMINFORM, Issue 27 2007Tang-Zhi Zhang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Regulation of the Flexibility of Planar Chiral [2.2]Paracyclophane Ligands and Its Significant Impact on Enantioselectivity in Asymmetric Reactions of Diethylzinc with Carbonyl Compounds.CHEMINFORM, Issue 51 2004Xun-Wei Wu Abstract For Abstract see ChemInform Abstract in Full Text. [source] ChemInform Abstract: Bidentate Planar Chiral ,6 -Arene Tricarbonyl Chromium(0) Complexes: Ligands for Catalytic Asymmetric Alkene Hydrosilylation.CHEMINFORM, Issue 1 2002Immo Weber Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Synthesis of Chiral 2-Phospha[3]ferrocenophanes and their Behaviour as Organocatalysts in [3+2],Cyclization ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2009Arnaud Voituriez Abstract Planar chiral 2-phospha[3]ferrocenophanes have been prepared via a stereoselective three-step synthesis. The key step is the lithiation of the 1,1,-disubstituted ferrocene 11 bearing (S)-2-(methoxymethyl)pyrrolidines as the chiral ortho -directing groups. The diastereoselectivity of these reactions has been mastered by an appropriate choice of the metallating agent, so as to afford a suitable access to C2 -symmetrical, tetrasubstituted ferrocenes. These compounds have been converted into the enantiomerically pure 2-phospha[3]-ferrocenophanes 16, via the corresponding acetates and their reactions with primary phosphines. Phosphines 16 have been used as nucleophilic catalysts in model cyclization reactions. Unlike 2-phospha[3]-ferrocenophanes with stereogenic ,-carbons, the planar chiral derivatives 16 proved to be suitable catalysts for these processes. Thus, for instance, phosphine 16c successfully promotes the enantioselective [3+2],annulations of allenes and enones into functionalized cyclopentenes (ees up to 96%). Among others, spirocyclic derivatives have been obtained in good yields and ees in the range 77,85%. The robustness of this catalyst has been demonstrated by recycling experiments. [source] Asymmetric Lithiation of Boron Trifluoride-Activated Aminoferrocenes: An Experimental and Computational InvestigationADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 11-12 2010Costa Metallinos Abstract Tertiary aminoferrocenes complexed to boron trifluoride (BF3) are shown to undergo asymmetric lithiation with alkyllithiums in the presence of bulky chiral 1,2-diaminocyclohexane ligands. This reaction represents the first BF3 -activated asymmetric lithiation of a prochiral aromatic amine and the first such transformation to be mediated by a chiral diamine other than (,)-sparteine. The process provides rapid access to a broad range of enantiomerically enriched 2-substituted-1-aminoferrocenes, including derivatives with uncommon substitution patterns that are of interest in catalysis. The enantioselectivity of the process is high enough (87:13 to 91:9 er) to allow for isolation of single enantiomers of several products after simple recrystallization as either the free aminoferrocenes or their ammonium fluoroborate salts. Both antipodes of the planar chiral 2-substituted-1-aminoferrocene products are accessible, as confirmed by single crystal X-ray diffraction analysis of two compounds with opposite relative stereochemistry. Single-point calculation of thirty-two different transition states of the reaction at the M06-2X/6-311+g(2d,2p) level produced a computational model that correctly predicted both the sense and extent of chiral induction. Three factors appeared to play important roles in determining enantioinduction during lithiation of BF3 -complexed tertiary aminoferrocenes: (i) the maintenance of a highly organized eight-membered ring transition state; (ii) the existence of a strong Li,,,F contact which placed the chiral diamine ligand in close proximity to the ferrocene substrate; (iii) the orientation of the sterically demanding N -alkyl groups of the chiral diamine additives, either away or towards, the aminoferrocene and the alkyllithium. The model may serve as a predictive tool for the rational design of new ligands for this and related asymmetric lithiations. [source] | ||||||||||