Palladium-catalyzed asymmetric allylic substitution using novel phosphino-ester (PHEST) ligands with 1,1′-binaphthyl skeleton

Kodama, Hidehiko; Taiji, Toshiji; Ohta, Tetsuo; Furukawa, Isao

doi:10.1016/s0957-4166(00)00370-0

Cited by 47 publications

(21 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[55] These two isomers are enantiomers in the case of the C 3 H 5 ligand and any other C 2v symmetric allyl moiety. As expected, the 31 …”

Section: Ligandsupporting

confidence: 86%

“…J(H,H) = 15 Hz) in this complex we conclude that the prefered geometry of the cinnamyl is trans with respect to the phosphorus atom and syn to the central allyl hydrogen atom. No other complexes are observed, as is confirmed by 31 P NMR spectroscopy, which shows one signal at 141.4 ppm. This confirms the assumption that the allyl moiety will orient itself in a fashion in which it experiences the least steric hindrance, that is, trans,syn to the bulky ligand.…”

Section: Full Papersupporting

confidence: 57%

“…The reports on application of chiral monodentate ligands in the allylic alkylation deal almost without exception with chiral phosphines. [24][25][26][27][28][29][30][31][32] In most cases the enantioselectivities obtained are at best in the same range as those observed for bidentate analogues. [26] Among the most prominent examples of successful monodentate ligands are the so-called MOP-type ligands (Scheme 2), introduced by Hayashi and co-workers.…”

Section: Introductionsupporting

confidence: 52%

See 2 more Smart Citations

Bulky Monodentate Phosphoramidites in Palladium‐Catalyzed Allylic Alkylation Reactions: Aspects of Regioselectivity and Enantioselectivity

Boele

Kamer

Lutz³

et al. 2004

Chemistry A European J

112

View full text Add to dashboard Cite

A series of bulky monodentate phosphoramidite ligands, based on biphenol, BINOL and TADDOL backbones, have been employed in the Pd‐catalysed allylic alkylation reaction. Reaction of disodium diethyl 2‐methyl malonate with monosubstituted allylic substrates in the presence of palladium complexes of the phosphoramidite ligands proceeds smoothly at room temperature. The regioselectivities observed depend strongly on the leaving group and the geometry of the allylic starting compounds. Mono‐coordination occurs when these ligands are ligated in [Pd(allyl)(X)] complexes (allyl=C3H5, 1‐CH3C3H4, 1‐C6H5C3H4, 1,3‐(C6H5)2C3H3; X=Cl, OAc). The solid‐state structure determined by X‐ray diffraction of [Pd(C3H5)(1)(Cl)] reveals a non‐symmetric coordination of the allyl moiety, caused by the stronger trans influence of the phosphoramidite ligand relative to X−. In all of these complexes, the syn,trans isomer is the major species present in solution. Because of fast isomerisation and high reactivity of the syn,cis complex, the major product formed upon alkylation is the linear product, especially for monosubstituted phenylallyl substrates in the presence of halide counterions. In the case of biphenol‐ and BINOL‐based phosphoramidites, however, a strong memory effect is observed when 1‐phenyl‐2‐propenyl acetate is employed as the substrate. In this case, nucleophilic attack competes effectively with the isomerisation of the transient cinnamylpalladium complexes. The asymmetric allylic alkylation of 1,3‐diphenyl‐2‐propenyl acetate afforded the chiral product in up to 93 % ee. Substrates with smaller substituents gave lower enantioselectivities. The observed stereoselectivity is explained in terms of a preferential rotation mechanism, in which the product is formed by attack on one of the isomers of the intermediate [Pd{1,3‐(C6H5)2C3H3}(L)(OAc)] complex.

show abstract

“…[55] These two isomers are enantiomers in the case of the C 3 H 5 ligand and any other C 2v symmetric allyl moiety. As expected, the 31 …”

Section: Ligandsupporting

confidence: 86%

Section: Full Papersupporting

confidence: 57%

Section: Introductionsupporting

confidence: 52%

See 1 more Smart Citation

Bulky Monodentate Phosphoramidites in Palladium‐Catalyzed Allylic Alkylation Reactions: Aspects of Regioselectivity and Enantioselectivity

Boele

Kamer

Lutz³

et al. 2004

Chemistry A European J

112

View full text Add to dashboard Cite

show abstract

“…[12] Experimental Section Optical yields of product 16 were determined using HPLC [(R,R)-WHELK-01 column) according to the literature. [16] Conversion of substrate 15 [17] and optical purity of products 17 [17] and 18 [18] were determined using HPLC (Daicel Chiralcel OD-H column) as described previously. Optical yields of product 19 were determined using HPLC (Chiralcel OD-H column) according to the literature.…”

Section: Discussionmentioning

confidence: 99%

Chiral Ionic Phosphites and Diamidophosphites: A Novel Group of Efficient Ligands for Asymmetric Catalysis

et al. 2007

View full text Add to dashboard Cite

Seven members of a new class of chiral P-monodentate cationic phosphites and diamidophosphites have been synthesized for the first time and tested as ligands in asymmetric transition metal catalysis. Up to 96 % ee was achieved in the rhodium-catalyzed asymmetric hydrogenation of functionalized olefins and up to 99 % ee in the palladium-catalyzed allylic allylation. Applications of the immobilized cationic rhodium complex to asymmetric catalytic synthesis have also been demonstrated.

show abstract

“…[50] Conversion of substrate 6 [51] and optical purity of products 8 [51] , 9 [52] and 10 [53] were determined using HPLC (Daicel Chiralcel OD-H column) as described previously. Conversion of substrate 11 and ee of product 12 were determined using HPLC (Daicel Chiralcel OD-H column) according to the literature.…”

Section: Methodsmentioning

confidence: 99%

MOP‐Type Binaphthyl Phosphite and Diamidophosphite Ligands and Their Application in Catalytic Asymmetric Transformations

et al. 2007

View full text Add to dashboard Cite

Monodentate phosphite and diamidophosphite ligands have been developed based on Omethyl-BINOL. These chiral ligands are easy to prepare from readily accessible phosphorylating re-The new ligands have demonstrated excellent enantioselectivity in the palladium-catalysed allylic substitution reactions of (E)-1,3-diphenylallyl acetate with sodium p-toluenesulfinate (up to 99 % ee), pyrrolidine (up to 97 % ee), dipropylamine (up to 95 % ee) and dimethyl malonate (up to 99 % ee). In the palladium-catalysed deracemization of ethyl (E)-1,3-diphenylallyl carbonate, up to 96 % enantioselectivity has been achieved. The diamidophosphite ligands have exhibited very good enantioselectivity in the Rh-catalysed asymmetric hydrogenation of dimethyl itaconate (up to 90 % ee).

show abstract

Palladium-catalyzed asymmetric allylic substitution using novel phosphino-ester (PHEST) ligands with 1,1′-binaphthyl skeleton

Cited by 47 publications

References 34 publications

Bulky Monodentate Phosphoramidites in Palladium‐Catalyzed Allylic Alkylation Reactions: Aspects of Regioselectivity and Enantioselectivity

Bulky Monodentate Phosphoramidites in Palladium‐Catalyzed Allylic Alkylation Reactions: Aspects of Regioselectivity and Enantioselectivity

Chiral Ionic Phosphites and Diamidophosphites: A Novel Group of Efficient Ligands for Asymmetric Catalysis

MOP‐Type Binaphthyl Phosphite and Diamidophosphite Ligands and Their Application in Catalytic Asymmetric Transformations

Contact Info

Product

Resources

About