The preparation of new palladium complexes in situ that were composed of a series of chiral diphosphite ligands, which were derived from (1S,2S)-trans-1,2-cyclohexanediol, have been described. It was found that (1S,2S)-bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphite-cyclohexanediol was the suitable ligand in the Pd-catalyzed allylic alkylation, and up to 75% ee for (E)-dimethyl 2-(1,3-diphenylallyl)malonate was obtained. In compared with the results of the asymmetric allylic alkylation, (1S,2S)-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphite-cyclohexanediol was proved to be the most efficient ligand in the Rh-catalyzed asymmetric hydrogenation of dimethyl itaconate and enamides with up to 99% ee. The stereochemically matched combinations between the diol skeleton and diaryl moieties of the ligands were essential for inducing high enantioselectivities in the two transformations. It was found that the sense of the enantiodiscrimination of the products was mainly determined by the configuration of the binaphthyl phosphite moieties.

A series of novel chiral diphosphite ligands have been synthesized from (1R,2R)-trans-1,2-cyclohexanediol, (1S,2S)-trans-1,2-cyclohexanediol, racemic trans-1,2-cyclohexanediol and chlorophosphoric acid diary ester, and were successfully employed in the Cu-catalyzed asymmetric 1,4-conjugate addition of diethylzinc to cyclohexenone with up to 99% ee. It was found that ligand 1,2-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediol 6a derived from racemic diol skeleton can show similar catalytic performance compared with ligand (1R,2R)-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediol 6a′ derived from enantiopure starting material. A significant dependence of stereoselectivity on the type of enone and the ring size of the cyclic enone was observed. Moreover, the configuration of the products was mainly determined by the configuration of the binaphthyl moieties of diphosphite ligands in the 1,4-addition of cyclic enones.Novel chiral diphosphite ligands derived from cyclohexanediol were synthesized and utilized in the Cu-catalyzed asymmetric conjugate addition of diethylzinc to cyclic enones.

Pd/TiN nanocomposite catalysts were fabricated for one-step selective hydrogenation of phenol to cyclohexanone successfully. High conversion of phenol (99%) and selectivity of cyclohexanone (98%) were obtained at 30 °C and 0.2 MPa H2 for 12 h in the mixed solvents of H2O and CH2Cl2. The Pd nanoparticles were stable in the reaction, and no aggregation was detected after four successive runs. The catalytic activity and selectivity depended on slightly the Pd particle sizes. The generality of the catalysts for this reaction was demonstrated by the selective hydrogenation of phenol derivatives, which showed that the catalyst was selective for the formation of cyclohexanone.Pd/TiN nanocomposite catalysts were fabricated by the chemical reduction with different Pd contents (1.3–8.5 wt%) and successfully used for the one-step selective hydrogenation of phenol and its derivatives.

A novel activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is presented to carry out the grafting copolymerization of lignin with styrene (St) and methyl methacrylate (MMA) using FeCl3·6H2O as a catalyst, PPh3 as a ligand and ascorbic acid (Vc) as a reducing agent for the first time. The synthesized lignin-based copolymers, L-g-PS and L-g-PMMA, were characterized by 1H NMR, FTIR, DSC, TGA and FE-SEM. 1H NMR showed the detailed structural conformation of the lignin and its copolymers, L-g-PS and L-g-PMMA. FTIR analysis confirmed that the PS and PMMA chains have been successfully grafted onto the lignin backbone. The DSC indicated that the graft copolymer had two Tg values and both of them are higher than those of the original lignin. TGA showed that the thermal stability of the graft copolymers, L-g-PS and L-g-PMMA, are very different from the original lignin. The surface properties and apparent structure of the lignin were completely changed after grafting with PS and PMMA chains. The GPC results showed narrow molecular weight distributions of the copolymers, which indicated that Fe(III)-catalyzed AGET ATRP for grafting copolymerization of lignin with St and MMA is well-controlled. The results obtained from these analytical methods confirm that grafting copolymerization has successfully occurred from the surface of the lignin, and Fe(III)-catalyzed AGET ATRP provide a novel, effective, and environment friendly method to synthesize lignin-based copolymers.

Direct C-3 arylation of imidazo[1,2-a]pyridines with aryl tosylates and mesylates has been accomplished by employing palladium(II) acetate associated with SPhos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) or L1 (2-(2-(diisopropylphosphino)phenyl)-1-methyl-1H-indole). This catalyst system can be applied to a wide range of aryl sulfonates and shows excellent C-3 regioselectivity of imidazo[1,2-a]pyridine. These results represent the first examples of using tosylate- and mesylate-functionalized arenes as the electrophile partners for this regioselective direct arylation.

A series of novel chiral diphosphite ligands was easily prepared in a few steps from commercial (1R,2R)-trans-1,2-cyclohexanediol as the chiral source, and successfully employed in the Rh-catalyzed asymmetric hydrogenation of α,β-unsaturated carboxylic acid derivatives and enamides with up to 99% ee for dimethyl itaconate and enamides and with up to 94% ee for α-dehydroamino acid esters. The stereochemically matched combination of (1R,2R)-trans-1,2-cyclohexanediol backbone and (S)-binaphthyl in the ligand (1R,2R)-bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediol, was essential for inducing high enantioselectivity. Moreover, the sense of enantiodiscrimination of the products was mainly determined by the configuration of the binaphthyl moieties.(1R,2R)-Bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediolC46H34O6P2[α]D25 = −499 (c 0.15, CH2Cl2)Source of chirality: (1R,2R)-trans-1,2-cyclohexanediol and BINOLAbsolute configuration: (1R,2R,Ra,Ra)(1R,2R)-Bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphitecyclohexanediolC46H34O6P2[α]D25 = +180 (c 0.18, CH2Cl2)Source of chirality: (1R,2R)-trans-1,2-cyclohexanediol and BINOLAbsolute configuration: (1R,2R,Sa,Sa)(1R,2R)-Bis[(R)-1,1′-H8-binaphthyl-2,2′-diyl]phosphitecyclohexanediolC46H50O6P2[α]D25 = −153 (c 0.11, CH2Cl2)Source of chirality: (1R,2R)-trans-1,2-cyclohexanediol and H8-BINOLAbsolute configuration: (1R,2R,Ra,Ra)(1R,2R)-Bis[(S)-1,1′-H8-binaphthyl-2,2′-diyl]phosphitecyclohexanediolC46H50O6P2[α]D25 = +170 (c 0.10, CH2Cl2)Source of chirality: (1R,2R)-trans-1,2-cyclohexanediol and H8-BINOLAbsolute configuration: (1R,2R,Sa,Sa)

Five novel tropos (3R,4R)- and/or (3S,4S)-N-benzyltartarimide-derived biphenylphosphite ligands were synthesized and applied in the Cu-catalyzed asymmetric conjugate addition of diethylzinc to cyclic enones with up to 75% e.e. Compared with the reported ligand 1-N-benzylpyrrolidine-3,4-bis[(R)-1,1’-binaphthyl-2,2’-diyl]phosphite-L-tartaric acid, the issue that L-(+)-tartaric acid backbone and (R)-binaphthyl showed strong matched/mismatched character was solved with these tropos ligands. It was found that the enantioselectivity was mainly controlled by the absolute configuration of N-benzyltartarimide backbone, and both enantiomers of the addition products can be obtained by simply changing the configuration of N-benzyltartarimide substituent.

A novel catalytic system for the hydrogenation of dimethyl itaconate has been developed by using rhodium–diphosphite complexes. These chiral diphosphite ligands were derived from glucopyranoside, d-mannitol derivatives, and binaphthyl or H8-binaphthyl phosphochloridites. The ligands based on the methyl 3,6-anhydro-α-d-glucopyranoside backbone and (R)- and (S)-binaphthol and/or (R)- and (S)-2,2′-dihydroxy-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthol gave almost complete conversion of the dimethyl itaconate and both enantiomers of dimethyl 2-methylsuccinate with excellent enantioselectivities. The stereochemically matched combination of methyl 3,6-anhydro-α-d-glucopyranoside and H8-(S)-binaphthyl in ligand 2,4-bis{[(S)-1,1′-H8-binaphthyl-2,2′-diyl]-phosphite} methyl 3,6-anhydro-α-d-glucopyranoside was essential to afford dimethyl 2-methylsuccinate with up to 98% ee. The sense of the enantioselectivity of products was predominantly determined by the configuration of the biaryl moieties of the ligands. An initial screening of [Rh(cod)2]BF4 with these ligands in the hydrogenation of (E)-2-(3-butoxy-4-methoxybenzylidene)-3-methylbutanoic acid was carried out. Good enantioselectivity (75% ee) and low yield for (R)-2-(3-butoxy-4-methoxybenzyl)-3-methylbutanoic acid were obtained.2,4-Bis{[(R)-1,1′-binaphthyl-2,2′-diyl] phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H34O9P2[α]D20=-321 (c 0.2, CH2Cl2)Source of chirality: d-glucose H8− BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Ra,Ra)2,4-Bis{[(S)-1,1′-binaphthyl-2,2′-diyl] phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H34O9P2[α]D20=+502 (c 0.2, CH2Cl2)Source of chirality: D-glucose and BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Sa,Sa)2,4-Bis{[(R)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H50O9P2[α]D20=-126 (c 0.2, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S, 2R, 3S, 4R, 5R, Ra, Ra)2,4-Bis{[(S)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H50O9P2[α]D20=+309 (c 0.2, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Sa,Sa)2,4-Bis{[(R)-1,1′-binaphthyl-2,2′-diyl] phosphite}-phenyl 3,6-anhydro-β-d-glucopyranosideC52H36O9P2[α]D20=-451 (c 0.2, CH2Cl2)Source of chirality: d-glucose and BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Ra,Ra)2,4-Bis{[(S)-1,1′-binaphthyl-2,2′-diyl] phosphite}-phenyl 3,6-anhydro-β-d-glucopyranosideC52H36O9P2[α]D20=+417 (c 0.2, CH2Cl2)Source of chirality: d-glucose and BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Sa,Sa)2,4-Bis{[(R)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-phenyl 3,6-anhydro-β-d-glucopyranosideC52H52O9P2[α]D20=-255 (c 0.4, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Ra,Ra)2,4-Bis{[(S)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-phenyl 3,6-anhydro-β-d-glucopyranosideC52H52O9P2[α]D20=+230 (c 0.4, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Sa,Sa)C58H52O10P21,2:5,6-Di-O-cyclohexylidene-3,4-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitol[α]D20=-365 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and BINOLAbsolute configuration: (2R,3R,4R,5R,Ra,Ra)1,2:5,6-Di-O-cyclohexylidene-3,4-bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitolC58H52O10P2[α]D20=+437 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and BINOLAbsolute configuration: (2R,3R,4R,5R,Sa,Sa)1,2:5,6-Di-O-cyclohexylidene-3,4-bis[(R)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC58H68O10P2[α]D20=-165 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Ra,Ra)1,2:5,6-Di-O-cyclohexylidene-3,4-bis[(S)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC58H68O10P2[α]D20=+184 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Sa,Sa)1,2:5,6-Di-O-isopropylidene-3,4-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H44O10P2[α]D20=-309 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and BINOLAbsolute configuration: (2R,3R,4R,5R,Ra,Ra)1,2:5,6-Di-O-isopropylidene-3,4-bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H44O10P2[α]D20=+496 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and BINOLAbsolute configuration: (2R,3R,4R,5R,Sa,Sa)1,2:5,6-Di-O-isopropylidene-3,4-bis[(R)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H60O10P2[α]D20=-205 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Ra,Ra)1,2:5,6-Di-O-isopropylidene-3,4-bis[(S)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H60O10P2[α]D20=+213 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Sa,Sa)

A series of novel bidentatephosphite ligands, derived from methyl 3,6-anhydro-α-d-glucopyranoside and chlorophosphoric acid diaryl ester, were easily synthesized. These ligands were successfully employed in the Cu-catalyzed asymmetric conjugate 1,4-addition of the organozinc reagents diethylzinc and/or dimethylzinc to enones. The stereochemically matched combination of glucopyranoside and (R)-H8-binaphthyl in ligand 2,4-bis{[(R)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-methyl 3,6-anhydro-α-d-glucopyranoside was essential to afford 85% ee for 3-ethylcyclohexanone with an (S)-configuration in THF, using Cu(OTf)2 as a catalytic precursor. When the reaction was carried out at lower temperatures, changing from −10 to −80 °C, a marginal influence of the temperature on the enantioselectivity of the reaction was observed. The presence of the methyl substituent at the 1-position of the glucopyranoside skeleton had a negative effect on the enantioselectivity in the 1,4-addition of ZnEt2 to acyclic enones.2,4-Bis{[(R)-1,1′-binaphthyl-2,2′-diyl]phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H34O9P2[α]D20=-321 (c 0.2, CH2Cl2)Source of chirality: d-glucose and BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Ra,Ra)2,4-Bis{[(S)-1,1′-binaphthyl-2,2′-diyl]phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H34O9P2[α]D20=+502 (c 0.2, CH2Cl2)Source of chirality: d-glucose and BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Sa,Sa)2,4-Bis{[(R)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H50O9P2[α]D20=-126 (c 0.2, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Ra,Ra)2,4-Bis{[(S)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite}-methyl 3,6-anhydro-α-d-glucopyranosideC47H50O9P2[α]D20=+309 (c 0.2, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Sa,Sa)

A series of chiral secondary alcohols were easily prepared by means of asymmetric hydrogenation of prochiral aromatic ketones using a new ((Rax)-BuP)/(R,R)-DPEN–Ru(II) complex catalyst system. The hydrogenation of 2-methylacetophenone in n-butanol (t-BuOK/Ru = 45.6/1, S/C = 500, 20 atm. of H2, 20 °C, 48 h) afforded (S)-1-(2′-methylphenyl)ethanol in 92% ee and >99% conversion.

Novel chiral diphosphite ligands derived from glucopyranoside and H8-binaphthol were synthesized, and successfully employed in the Cu-catalyzed asymmetric 1,4-addition of organozinc reagents dimethylzinc, diethylzinc, and diphenylzinc to cyclic and acyclic enones with up to 96% ee. The stereochemically matched combination of d-glucopyranoside backbone and (R)-H8-binaphthyl in the ligand 2,4-bis{[(R)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-phenyl 3,6-anhydro-β-d-glucopyranoside was essential for inducing high enantioselectivity. A significant dependence of stereoselectivity on the type of enones and the ring size of cyclic enones was observed. Moreover, the sense of the enantiodiscrimination of the products was mainly determined by the configuration of the H8-binaphthyl moieties.2,4-Bis{[(R)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-phenyl 3,6-anhydro-β-d-glucopyranosideC52H52O9P2[α]D20=-255 (c 0.4, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Ra,Ra)2,4-Bis{[(S)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite}-phenyl 3,6-anhydro-β-d-glucopyranosideC52H52O9P2[α]D20=+230 (c 0.4, CH2Cl2)Source of chirality: d-glucose and H8-BINOLAbsolute configuration: (1S,2R,3S,4R,5R,Sa,Sa)

A series of novel chiral diphosphite ligands have been synthesized from d-mannitol derivatives and chlorophosphoric acid diary ester, and were successfully employed in the copper catalyzed enantioselective conjugate addition of organozinc reagents diethylzinc and dimethylzinc to cyclic and acyclic enones. The stereochemically matched combination of d-mannitol and (R)-H8-binaphthyl in ligand 1,2:5,6-di-O-isopropylidene-3,4-bis[(R)-1,1′-H8-binaphthyl-2,2′-diyl] phosphite-d-mannitol was essential to afford 93% ee for 3-ethylcyclohexanone, 92% ee for 3-ethylcyclopentanone, and 90% ee for 3-ethylcycloheptanone in toluene, using Cu(OTf)2 as a catalytic precursor. The results clearly indicated that the chiral organocopper reagent exhibited high enantioselectivies for cyclic enones bearing different ring sizes. As for the backbone of this type of ligand, it has been demonstrated that 1,2:5,6-di-O-isopropylidene-d-mannitol was more efficient than 1,2:5,6-di-O-cyclohexylidene-d-mannitol. The sense of the enantiodiscrimination was mainly determined by the configuration of the diaryl phosphite moieties in the 1,4-addition of cyclic enones.1,2:5,6-Di-O-cyclohexylidene-3,4-bis[(R)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC58H68O10P2[α]D20=-165 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Ra,Ra)1,2:5,6-Di-O-cyclohexylidene-3,4-bis[(S)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC58H68O10P2[α]D20=+184 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Sa,Sa)1,2:5,6-Di-O-isopropylidene-3,4-bis[(R)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H44O10P2[α]D20=-309 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and BINOLAbsolute configuration: (2R,3R,4R,5R,Ra,Ra)1,2:5,6-Di-O-isopropylidene-3,4-bis[(S)-1,1′-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H44O10P2[α]D20=+496 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and BINOLAbsolute configuration: (2R,3R,4R,5R,Sa,Sa)1,2:5,6-Di-O-isopropylidene-3,4-bis[(R)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H60O10P2[α]D20=-205 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Ra,Ra)1,2:5,6-Di-O-isopropylidene-3,4-bis[(S)-1,1′-H8-binaphthyl-2,2′-diyl]phosphite-d-mannitolC52H60O10P2[α]D20=+213 (c 0.2, CH2Cl2)Source of chirality: d-mannitol and H8-BINOLAbsolute configuration: (2R,3R,4R,5R,Sa,Sa)