Rational Design and Synthesis of [5]Helicene-Derived Phosphine Ligands and Their Application in Pd-Catalyzed Asymmetric Reactions.
A series of novel optically active [5]helicene-derived phosphine ligands (L1, with a 7,8-dihydro[5]helicene core structure- and L2, with a fully aromatic [5]helicene core structure) were synthesized. Despite their structural similarities, L1 and L2 exhibit particularly different characteristics in their use as chiral ligands. L1 was highly effective in the asymmetric allylation of indoles with 1,3-diphenylallyl acetate (up to 99% ee), and in the etherification of alcohols (up to 96% ee). In contrast, L2 was highly effective in the stereocontrol of helical chirality in Suzuki-Miyaura coupling (SMC) reaction (up to 99% ee). Density functional theory analysis was employed to propose a model that accounts for the origin of the enantioselectivity in these reactions.
Graduate School of Pharmaceutical Sciences, Kyushu University, Fukuoka, 812-8582, Japan.
Kosuke
K
Yamamoto
Graduate School of Pharmaceutical Sciences, Kyushu University, Fukuoka, 812-8582, Japan.
Takashi
T
Shimizu
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, 816-8580, Japan.
Kazunobu
K
Igawa
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, 816-8580, Japan.
Katsuhiko
K
Tomooka
Graduate School of Pharmaceutical Sciences, Kyushu University, Fukuoka, 812-8582, Japan.
Go
G
Hirai
Graduate School of Pharmaceutical Sciences, Kyushu University, Fukuoka, 812-8582, Japan.
Hiroshi
H
Suemune
Graduate School of Pharmaceutical Sciences, Kyushu University, Fukuoka, 812-8582, Japan.
Kazuteru
K
Usui
D002384:Catalysis; D015195:Drug Design; D008024:Ligands; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry; D011083:Polycyclic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D008024:Ligands; D010720:Phosphines; D011083:Polycyclic Compounds; C031660:helicenes; D010165:Palladium