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The chloro alcohols 4-6 derived from TADDOLs (=alpha,alpha, alpha?,alpha?-tetraaryl-1,3-dioxolan-4,5-dimethanols) are used to prepare corresponding sulfanyl alcohols, ethers, and amines (Scheme 1 and Table 1). The dithiol analog of TADDOL and derivatives thereof, 45-49, were also synthesized. The crystal structures of 16 representatives of this series of compounds are reported (Figs. 1-3 and Scheme 2). The thiols were employed in Cu-catalyzed enantioselective conjugate additions of Grignard reagents to cyclic enones, with cycloheptenone giving the best results (er up to 94:6). The enantioselectivity reverses from Si-addition with the sulfanyl alcohol to Re-addition with the alkoxy or dimethylamino thiols (Table 4). Cu I-Thiolates, 50-53, could be isolated in up to 84% yield (Scheme 2) and were shown to have tetranuclear structures in the gas phase (by ESI-MS), in solution (CH2Cl2, THF; by vapor-pressure osmometry and by NMR pulsed-gradient diffusion measurements; Table 5), and in the solid state (X-ray crystal structures in Scheme 2). The Cu complex 50 of the sulfanyl alcohol is stable in air and in the presence of weak aqueous acid, and it is a highly active catalyst (0.5 mol-%) for the 1,4-additions, leading to the same enantio- and regioselectivities observed with the in situ generated catalyst (6.5 mol-%; Scheme 3). Since the reaction mixtures contain additional metal salts (MgX2, LiX) it is not possible at this stage, to propose a mechanistic model for the conjugate additions. Copyright

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A recently reported Pd0-catalyzed asymmetric Nazarov-type cyclization has been successfully applied in the key step of the first catalytic asymmetric total synthesis of (-)-rocaglamide (natural) and (+)-rocaglamide. The stereochemistry at the C3 position that controls the stereochemistry of all other stereocenters is determined in the cyclization step. This versatile and modular synthesis proceeds from simple reagents.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Treatment in the solid state of inclusion compounds of ketones in optically active host molecules with a BH3-ethylenediamine complex gave optically active alcohols.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Bronsted acid-catalyzed dihydroxylation of olefins in aqueous medium

The trans-dihydroxylation of olefins occurs efficiently by aqueous hydrogen peroxide catalyzed by p-toluenesulfonic acid at 50C, allowing the catalyst reuse and an outstanding substrate functional group tolerance such as tert-butoxycarbonylamino (BocNH), benzyloxycarbonylamino (CbzNH), benzyloxy (OBn), tosyloxy (OTs), hindered ketal, (2-trimethylsilyl)ethoxymethoxy (OSEM), benzylamino (NBz), benzyloxy (OBz) and free amino acid. Copyright

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Development of Enantioselective Palladium-Catalyzed Alkene Carboalkoxylation Reactions for the Synthesis of Tetrahydrofurans

The Pd-catalyzed coupling of gamma-hydroxyalkenes with aryl bromides affords enantiomerically enriched 2-(arylmethyl)tetrahydrofuran derivatives in good yield and up to 96:4 e.r. This transformation was achieved through the development of a new TADDOL/2-arylcyclohexanol-derived chiral phosphite ligand. The transformations are effective with an array of different aryl bromides, and can be used for the preparation of products bearing quaternary stereocenters.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Enantioselective allyltitanation of aldehydes with cyclopentadienylialkoxyallylitanium complexes

The preparation, analysis, and reactions of novel, highly stereoselective cyclopentadienyldialkoxyallyltitanium reagents, available in both enamiomeric forms, are described. Chiral monochlorotitanates are readily prepared from CpTiCl3 or Cp*TiCl3 and chiral 1,4-diols, which in turn are obtained from tartrate ester acetals by Grignard addition. The resulting stable seven-membered titanacycles have been analyzed by 1H, 13C, and 49Ti NMR spectroscopy. The structures of two representatives, the complexes 15 and 20, are confirmed by X-ray diffraction. The allyl reagents are obtained from the chlorides by transmetalation with allyllithium, allylpotassium, or allyl Grignard compounds. For the ensuing reactions with aldehydes these reagents do not have to be isolated or purified. Correlation of X-ray data and Ti NMR line widths with selectivity suggests that asymmetric distortion of the titanium coordination geometry could be essential for enantioface discrimination, rather than direct interactions of reactants with the chiral ligand. By variation of the ligand substituents, allyltitanates derived from chloride 15 (with 2,2-dimethyl-alpha,alpha,alpha?,alpha?-tetraphenyl-1,3- dioxolane-3,4-dimethanol as the ligand) emerged as the most selective reagents. Excellent regio-, diastereo-, and enantioselectivities (usually ?95% ee, ?95% de) are obtained for reactions with various achiral and chiral aldehydes. The NMR spectra of the allyl and the crotyl complexes (R,R)-9 and (R,R)-29 exhibit fast 1,3-shifts, favoring the (E) isomer with titanium eta1-bound to the unsubstituted allyl terminus. This equilibration, and also the equilibrations of other aryl-, alkoxy-, and silyl-substituted allyltitanium complexes, restricts this method to the preparation of branched regioisomers with the anti configuration.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Synthesis and Reactivity of Chiral, Wide-Bite-Angle, Hybrid Diphosphorus Ligands

Effective and modular synthetic approaches toward phosphine-phosphite ligands and phosphine-phosphonite ligands featuring a diphenyl ether backbone have been developed. The phosphine-phosphite ligands are obtained by a two-step protocol from 2-bromo-2?-methoxydiphenyl ether. The phosphine-phosphonite ligands are prepared in a four-step synthetic protocol that involves a novel, unsymmetrical diphenyl ether derived phosphine-phosphorusdiamide as key building block. Structural studies on PtII complexes with either phosphine-phosphite or phosphine-phosphonite ligands indicate strict cis coordination for these ligand systems. High-pressure NMR spectroscopy studies of Rh complexes under syngas indicate the presence of two ea isomers for Rh(H)(CO)2(PP). The existence of this mixture is further supported by high-pressure IR spectroscopy studies. In order to benchmark the activity and selectivity of these novel, wide-bite-angle, mixed-donor ligands, they were screened in Pd-catalyzed asymmetric allylic alkylation as well as Rh-catalyzed hydrogenation and hydroformylation reactions. The ligands give 100-% conversion and low-to-moderate enantioselectivity in the allylic alkylation of 1,3-diphenyl-2-propenyl acetate and cyclohexyl-2-enyl acetate with dimethyl malonate. In the hydroformylation of styrene, good conversion and regioselectivities are achieved but only moderate enantioselectivity. The ligands give good conversions in asymmetric hydrogenation of typical substrates, with good-to-excellent enantioselectivities of up to 97-% depending on the substrate. Copyright

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI