Enantioselective elimination reaction of a 6,6-membered bicyclic allylic carbonate. Importance of chirality reversal depending on the palladium-chiral phosphine ratio

Shimizu, Isao; Matsumoto, Yoshiyuki; Shoji, Ken; Ono, Takehiko; Satake, Akiharu; Yamamoto, Akio

doi:10.1016/0040-4039(96)01587-0

Cited by 31 publications

(18 citation statements)

References 21 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Enantioreversion has been previously observed with several ligands for different reasons. [22][23][24][25][26][27][28] For instance, the molar ratio between components 22 or changing the reaction solvent 25 can cause the reversal of the enantioselectivity of certain catalysts. Immobilising on polymer supports has also been described to produce reverse enantioselectivity.…”

Section: Catalytic Testsmentioning

confidence: 99%

Modification of chiral dimethyl tartrate through transesterification: Immobilization on POSS and enantioselectivity reversal in sharpless asymmetric epoxidation

et al. 2009

View full text Add to dashboard Cite

Modification of dimethyl tartrate has been investigated through transesterification with aminoalcohols to provide reactive functionalities for the covalent bonding of chiral tartrate to polyhedral oligomeric silsesquioxanes. The transesterification of dimethyl tartrate has been widely studied using different catalytic systems and reaction conditions. Through the proper selection of both the catalytic system and the reaction conditions, it is possible to achieve monosubstituted or bis-substituted tartrate derivatives as sole products. All the intermediate chiral tartrate-derived ligands were successfully used in the homogeneous enantioselective epoxidation of allylic alcohols providing moderate enantiomeric excess over the products. Attached amine groups have been used to support the modified tartrate ligands on to a haloaryl-functionalized silsesquioxane moiety. This final chiral tartrate ligand displays reverse enantioselectivity in the asymmetric epoxidation of allylic alcohols with regard to the starting dimethyl tartrate ligand, both molecules having the same chiral sign. However, the POSS-containing ligand can be easily recovered in almost quantitative yield and reused in asymmetric epoxidation reactions. In addition, recovered silsesquioxane-pendant ligand, though displaying decreasing catalytic activity in recycling epoxidation tests, showed very stable enantioselective behavior.

show abstract

Section: Catalytic Testsmentioning

confidence: 99%

Modification of chiral dimethyl tartrate through transesterification: Immobilization on POSS and enantioselectivity reversal in sharpless asymmetric epoxidation

et al. 2009

View full text Add to dashboard Cite

show abstract

“…[12] We now demonstrate that BINAP(O) behaves completely differently to BINAP in representative enantioselective intermolecular Mizoroki-Heck reactions. Both the regio-and enantioselectivity [17] of the transformations are markedly influenced. …”

Section: Introductionmentioning

confidence: 98%

BINAP versus BINAP(O) in Asymmetric Intermolecular Mizoroki–Heck Reactions: Substantial Effects on Selectivities

Wöste

Oestreich

2011

Chemistry A European J

View full text Add to dashboard Cite

2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP) was employed as chiral ligand in the enantioselective intermolecular Mizoroki-Heck reaction, whereas the use of cognate BINAP(O) (monooxidized BINAP) is unprecedented. The regio- and enantioselectivity of the arylation of representative cyclic alkenes changes dramatically in the presence of hemilabile BINAP(O) instead of BINAP. The arylation of 2,3-dihydrofuran is perfectly regiodivergent (98:2 versus 0:100) and the arylation of cyclopentene is only enantioselective with BINAP(O) [60 versus 10% enantiomeric excess (ee)]. Use of [Pd(2)(dba)(3)]⋅dba (dba=dibenzylideneacetone) instead of Pd(OAc)(2) produces as high as 86% ee in the arylation of cyclopentene.

show abstract

“…In fact, different reactivities have been observed with the utilization of BPMO ligands compared to their cognate bidentate bis-phosphine ligands. 4 Significantly, in several examples, the bis-phosphine mono-oxide provides the opposite 5 or enhanced 6 enantioselection in asymmetric synthesis. In other cases, the BPMO ligands have also proved to be catalytically superior compared to the parent bis-phosphine.…”

Section: Introductionmentioning

confidence: 99%

A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions

Hyde

et al. 2017

Chem. Sci.

View full text Add to dashboard Cite

show abstract

Enantioselective elimination reaction of a 6,6-membered bicyclic allylic carbonate. Importance of chirality reversal depending on the palladium-chiral phosphine ratio

Cited by 31 publications

References 21 publications

Modification of chiral dimethyl tartrate through transesterification: Immobilization on POSS and enantioselectivity reversal in sharpless asymmetric epoxidation

Modification of chiral dimethyl tartrate through transesterification: Immobilization on POSS and enantioselectivity reversal in sharpless asymmetric epoxidation

BINAP versus BINAP(O) in Asymmetric Intermolecular Mizoroki–Heck Reactions: Substantial Effects on Selectivities

A rational pre-catalyst design for bis-phosphine mono-oxide palladium catalyzed reactions

Contact Info

Product

Resources

About