Abstract
The design and development of new chiral ligands to enable precise stereocontrol in a wide variety of reactions is one of the most important branches of organic synthesis. To date, the development of hybrid ligands containing both σ-donating and π-donating groups has attracted considerable attention, with unprecedented reactivities and stereoselectivities being observed. Therefore to develop efficient hybrid chiral ligands with novel structural motifs, we envisage that helicene would be a suitable π-donor efficiently to construct a helical environment around a metal center. In this context, we herein describe our recent efforts to develop a series of novel chiral [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). The prepared ligands, and in particular L1, were found highly effective in the asymmetric allylation of 1,3-diphenylallyl acetate with indoles and etherification with alcohols. Furthermore, in the asymmetric Suzuki-Miyaura coupling reaction, L2 exhibited excellent enantioselectivities. Finally, density functional theory studies were employed to propose a model that accounts for the origin of such high enantioselectivity in these reactions.
| Original language | Japanese |
|---|---|
| Pages (from-to) | 1381-1390 |
| Number of pages | 10 |
| Journal | Yakugaku Zasshi |
| Volume | 137 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Nov 1 2017 |
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螺旋空間を利用した新規不斉リン配位子の開発と不斉触媒反応への応用. / Usui, Kazuteru.
In: Yakugaku Zasshi, Vol. 137, No. 11, 01.11.2017, p. 1381-1390.Research output: Contribution to journal › Article
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TY - JOUR
T1 - 螺旋空間を利用した新規不斉リン配位子の開発と不斉触媒反応への応用
AU - Usui, Kazuteru
PY - 2017/11/1
Y1 - 2017/11/1
N2 - The design and development of new chiral ligands to enable precise stereocontrol in a wide variety of reactions is one of the most important branches of organic synthesis. To date, the development of hybrid ligands containing both σ-donating and π-donating groups has attracted considerable attention, with unprecedented reactivities and stereoselectivities being observed. Therefore to develop efficient hybrid chiral ligands with novel structural motifs, we envisage that helicene would be a suitable π-donor efficiently to construct a helical environment around a metal center. In this context, we herein describe our recent efforts to develop a series of novel chiral [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). The prepared ligands, and in particular L1, were found highly effective in the asymmetric allylation of 1,3-diphenylallyl acetate with indoles and etherification with alcohols. Furthermore, in the asymmetric Suzuki-Miyaura coupling reaction, L2 exhibited excellent enantioselectivities. Finally, density functional theory studies were employed to propose a model that accounts for the origin of such high enantioselectivity in these reactions.
AB - The design and development of new chiral ligands to enable precise stereocontrol in a wide variety of reactions is one of the most important branches of organic synthesis. To date, the development of hybrid ligands containing both σ-donating and π-donating groups has attracted considerable attention, with unprecedented reactivities and stereoselectivities being observed. Therefore to develop efficient hybrid chiral ligands with novel structural motifs, we envisage that helicene would be a suitable π-donor efficiently to construct a helical environment around a metal center. In this context, we herein describe our recent efforts to develop a series of novel chiral [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). The prepared ligands, and in particular L1, were found highly effective in the asymmetric allylation of 1,3-diphenylallyl acetate with indoles and etherification with alcohols. Furthermore, in the asymmetric Suzuki-Miyaura coupling reaction, L2 exhibited excellent enantioselectivities. Finally, density functional theory studies were employed to propose a model that accounts for the origin of such high enantioselectivity in these reactions.
U2 - 10.1248/yakushi.17-00151
DO - 10.1248/yakushi.17-00151
M3 - 記事
C2 - 29093375
VL - 137
SP - 1381
EP - 1390
JO - Yakugaku Zasshi
JF - Yakugaku Zasshi
SN - 0031-6903
IS - 11
ER -