Asymmetric Hydrogenation of Quinoxalines, Benzoxazines, and a Benzothiazine Catalyzed by Chiral Ruthenabicyclic Complexes

被引：37

作者：

Arai, Noriyoshi ^{[1
,2
]}

Saruwatari, Yu ^{[1
,2
]}

Isobe, Kotaro ^{[1
,2
]}

Ohkuma, Takeshi ^{[1
,2
]}

机构：

[1] Hokkaido Univ, Div Chem Proc Engn, Fac Engn, Sapporo, Hokkaido 0608628, Japan

[2] Hokkaido Univ, Frontier Chem Ctr, Fac Engn, Sapporo, Hokkaido 0608628, Japan

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2013年 / 355卷 / 14-15期

基金：

日本学术振兴会;

关键词：

amines; asymmetric catalysis; hydrogenation; imines; ruthenium; ENANTIOSELECTIVE HYDROGENATION; STEREOSELECTIVE HYDROGENATION; ANTIBACTERIAL ACTIVITIES; DIPHOSPHINE LIGANDS; FOLIC-ACID; MECHANISM; 2-METHYLQUINOXALINE; REDUCTION; POTENT;

D O I：

10.1002/adsc.201300604

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The ruthenabicyclic complex RuCl[(R)-daipena][(R)-dm-segphos] with potassium tert-butoxide catalyzes the hydrogenation of 2-alkylquinoxalines and a 3-methyl-2H-1,4-benzoxazine in toluene under 20-100atm of hydrogen at 40 degrees C to afford S-configured cyclic amino products in greater than 97% enantiomeric excess {DAIPENA=anion of DAIPEN at the 2-position of an anisyl group, DAIPEN=1,1-di(4-anisyl)-2-isopropyl-1,2-ethylenediamine, DM-SEGPHOS=(4,4-bi-1,3-benzodioxole)-5,5-diylbis[di(3,5-xylyl)phosphine]}. The high catalytic activity results in a turnover number as high as 9400. Hydrogenation of the benzoimine heterocycles with the RuCl[(R)-daipena][(R)-segphos]/potassium tert-butoxide system yields the R-configured products in high enantiomeric excess [SEGPHOS=(4,4-bi-1,3-benzodioxole)-5,5-diylbis(diphenylphosphine)]. The mode of enantioselection is discussed based on transition state models involving six-membered pericyclic structures.

引用

页码：2769 / 2774

页数：6

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