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

Translated title of the contribution: Development of New Chiral Phosphine Ligands with Helical Environments and Their Application in Asymmetric Catalytic Reactions

Kazuteru Usui

Research output: Contribution to journalArticle

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 languageJapanese
Pages (from-to)1381-1390
Number of pages10
JournalYakugaku Zasshi
Volume137
Issue number11
DOIs
Publication statusPublished - Nov 1 2017

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phosphine
Ligands
Indoles
Synthetic Chemistry Techniques
Acetates
Metals
Alcohols

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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 journalArticle

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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.",
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