Catalytic Asymmetric Synthesis with Rh−Diene Complexes:  1,4-Addition of Arylboronic Acids to Unsaturated Esters

2005 ◽  
Vol 7 (17) ◽  
pp. 3821-3824 ◽  
Author(s):  
Jean-François Paquin ◽  
Corey R. J. Stephenson ◽  
Christian Defieber ◽  
Erick M. Carreira
Keyword(s):  
Asymmetric Synthesis ◽  
Unsaturated Esters ◽  
Arylboronic Acids ◽  
Catalytic Asymmetric Synthesis ◽  
Catalytic Asymmetric

scholarly journals Catalytic Asymmetric Synthesis with Rh—Diene Complexes: 1,4-Addition of Arylboronic Acids to Unsaturated Esters.

ChemInform ◽  
2006 ◽  
Vol 37 (1) ◽  
Author(s):  
Jean-Francois Paquin ◽  
Corey R. J. Stephenson ◽  
Christian Defieber ◽  
Erick M. Carreira
Keyword(s):  
Asymmetric Synthesis ◽  
Unsaturated Esters ◽  
Arylboronic Acids ◽  
Catalytic Asymmetric Synthesis ◽  
Catalytic Asymmetric

Catalytic asymmetric reactions using environmentally friendly reagents and catalyst: Asymmetric synthesis versus kinetic resolution

2006 ◽  
Vol 78 (11) ◽  
pp. 2029-2034 ◽  
Author(s):  
Kiyoshi Tomioka
Keyword(s):  
Asymmetric Synthesis ◽  
Kinetic Resolution ◽  
Point Of View ◽  
High Yield ◽  
Compound A ◽  
Arylboronic Acids ◽  
Catalytic Asymmetric Synthesis ◽  
Product Mixture ◽  
Starting Compound ◽  
Catalytic Asymmetric

Kinetic resolution of racemic compounds is a familiar method for the preparation of optically active compounds. However, an inevitable and critical drawback from the point of view of green chemistry is the consequent wastage of half of the starting compound. A catalytic asymmetric synthesis of 5-arylcyclohex-2-enones was developed starting from racemic 5-(trimethylsilyl)cyclohex-2-enone, which overcomes the drawback of kinetic resolution. A chiral amidophosphane- or BINAP-Rh(I)-catalyzed asymmetric conjugate arylation of racemic 5-(trimethylsilyl)cyclohex-2-enone with arylboronic acids in dioxane-water (10:1) afforded trans- and cis-3-aryl-5-(trimethylsilyl)cyclohexanones in reasonably high enantioselectivity. Dehydrosilylation of the product mixture with Cu(II) chloride in dimethylformamide (DMF) gave 5-arylcyclohex-2-enones with up to 93 % ee in high yield. Enantiofacial selectivity with chiral phosphane-Rh(I) overrides the trans-diastereoselectivity that is maintained in the achiral or racemic phosphane-Rh(I)-catalyzed conjugate arylation of 5-(trimethylsilyl)cyclohex-2-enone.

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