Asymmetric synthesis of 5-arylcyclohexenones by rhodium(I)-catalyzed conjugate arylation of racemic 5-(trimethylsilyl)cyclohexenone with arylboronic acids.
[reaction: see text] A catalytic asymmetric conjugate arylation of racemic 5-(trimethylsilyl)cyclohex-2-enone with arylboronic acids was catalyzed by 3 mol % chiral amidophosphane- or BINAP-Rh(I) in dioxane-water (10:1) to afford trans- and cis-3-aryl-5-(trimethylsilyl)cyclohexanones in high enantioselectivity. Dehydrosilylation of the product mixture with cupric chloride in DMF gave 5-arylcyclohex-2-enones with up to 93% ee in good yield. Enantiofacial selectivity with chiral phosphane-Rh(I) exceeds the trans-diastereoselectivity that is maintained in the achiral or racemic phosphane-Rh(I)-catalyzed conjugate arylation of 5-(trimethylsilyl)cyclohexenone.
Chen
Qian
Q
Graduate School of Pharmaceutical Sciences, Kyoto University, Yoshida, Sakyo-ku, Kyoto 606-8501, Japan.
Kuriyama
Masami
M
Soeta
Takahiro
T
Hao
Xinyu
X
Yamada
Ken-ichi
K
Tomioka
Kiyoshi
K
D001897:Boronic Acids / Q000737:chemistry*; D002384:Catalysis; D003512:Cyclohexanones / Q000138:chemical synthesis / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D007536:Isomerism; D008024:Ligands; D008745:Methylation; D015394:Molecular Structure; D010720:Phosphines / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry*
D001897:Boronic Acids; D003512:Cyclohexanones; D008024:Ligands; D010720:Phosphines; D006859:Hydrogen; D012238:Rhodium; C044646:phosphine