Asymmetric transfer hydrogenation of prochiral .ALPHA.,.BETA.-unsaturated acids and their esters by achiral or chiral alcohols with ruthenium chiral diphosphine complexes.

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概要

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• Asymmetric transfer hydrogenations of α,β-unsaturated acids (MeCH=C(Me)CO<SUB>2</SUB>H, PhCH=C(Me)CO<SUB>2</SUB>H, CH<SUB>2</SUB>=C(CH<SUB>2</SUB>CO<SUB>2</SUB>H)CO<SUB>2</SUB>H, and HO<SUB>2</SUB>CCH=C(Me)CO<SUB>2</SUB>H) and esters (MeCH=C(Me)CO<SUB>2</SUB>R; R=achiral and chiral group) by alcohols (PhCH<SUB>2</SUB>OH, (<I>RS</I>)-PhCH(Me)OH, and α-D-glucofuranose derivatives) were carried out with RuCl<SUB>2</SUB>(PPh<SUB>3</SUB>)<SUB>3</SUB> or Ru<SUB>2</SUB>Cl<SUB>4</SUB>((+) or (−)-diop)<SUB>3</SUB> (diop=2,3-<I>O</I>-isopropylidene-1,4-bis(diphenylphosphino)-2,3-butanediol) at 160–190 °C. The optical purity (3.4–16.4%) of hydrogenated acids obtained with PhCH<SUB>2</SUB>OH and Ru<SUB>2</SUB>Cl<SUB>4</SUB>((−)-diop)<SUB>3</SUB> is in the order MeCH=C(Me)CO<SUB>2</SUB>H>PhCH=C(Me)CO<SUB>2</SUB>H>CH<SUB>2</SUB>=C(CH<SUB>2</SUB>CO<SUB>2</SUB>H)CO<SUB>2</SUB>H>HO<SUB>2</SUB>CCH=C(Me)CO<SUB>2</SUB>H, suggesting that the substrates possessing two carboxyl groups would provide an asymmetrically unfavorable coordination to the Ru(II) complex for this asymmetric reaction. In the transfer hydrogenation of MeCH=C(Me)CO<SUB>2</SUB>R by PhCH<SUB>2</SUB>OH or (<I>RS</I>)-PhCH(Me)OH at 190 °C, the extent of asymmetric induction of Ru<SUB>2</SUB>Cl<SUB>4</SUB>((−)-diop)<SUB>3</SUB> (1.7–11.4% e.e. with PhCH<SUB>2</SUB>OH and 7.4–18.2% e.e. with (<I>RS</I>)-PhCH(Me)OH) decreases with increase in bulkiness of groups R (R=H, Me, Et, <I>n</I>-Bu, and PhCH<SUB>2</SUB>) and is not enhanced by the introduction of any groups R with chiral carbon atoms into esters (maximum 15.4% e.e.). The structural change of hydrogen donors from PhCH<SUB>2</SUB>OH to (<I>RS</I>)-PhCH(Me)OH appreciably increases the optical purity of the saturated acids and esters, and the chiral α-D-glucofuranose derivatives afford optically active saturated products, even with achiral RuCl<SUB>2</SUB>(PPh<SUB>3</SUB>)<SUB>3</SUB>. Features of the present reaction are discussed in relation to the reaction mechanism.

• 公益社団法人 日本化学会の論文

著者

• OHKUBO Katsutoshi

  Department of Applied Chemistry and Biochemistry, Faculty of Engineering, Kumamoto University

• Yoshinaga Kohji

  Department Of Applied Chemistry Faculty Of Engineering Kyushu Institute Of Technology

• Kito Taketoshi

  Department Of Chemistry Kyushu Institute Of Technology.

• Yoshinaga Kohji

  Department of Material Engineering, Kyushu Institute of Technology

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