Efficient dynamic kinetic resolution of secondary alcohols with a novel tetrafluorosuccinato ruthenium complex

Research Advances of the Chiral Binap-Ru(II) Catalysts in Asymmetric Hydrogenation Reactions

“…1996 年, Takaya 课题组 [110] [111] 合 成 了钌 团簇 化 合物 2006 年, Hulshof 课题组 [112] 1999 年 , Genet 课 题 组 [115] 2004 年, Lemaire 课题组 [117] 研究了[Ru(benzene)- 2002 年, Pregosin 课题组 [118] 2006 年, 他们 [130] 继续研究发现, 在 60 ℃下, 在体 积比为 3∶1 的乙醇/1,4-二氧己环混合溶剂中, 使用 随后, 他们 [133] 报道合成了一系列具有"夹心"多 层结构的手性树枝状[RuCl 2 (Binap)(dpen)]类型催化剂, 并研究了其在简单芳香酮不对称加氢中的催化性能, 研 究表明此类催化剂与小分子[RuCl 2 (Binap)(dpen)]催化剂 的催化效果相当, 这说明催化剂表面 Fréchet 树枝的生 成对催化剂的对映选择性没有明显影响. 此外, 此类催 化剂可重复使用九次而没有对映选择性的降低(Eq.…”

Chemoenzymatic and microbial dynamic kinetic resolutions

“…Hulshof and coworkers 55 reported the DKR of five different substrates of secondary alcohols using dinuclear ruthenium complex, bearing tetrafluorosuccinate and (rac)-BINAP ligands as the racemization catalyst. The DKR was successfully carried out for the aromatic alcohol (1-phenylethanol (44)), an aliphatic secondary alcohol (2-octanol), an aromatic alcohol bearing an electron-withdrawing substituent on the phenyl ring (a-methyl-4-(trifluoromethyl)benzyl alcohol), an aromatic alcohol bearing an electrondonating substituent on the ring (a-methyl-4-methoxybenzyl alcohol) and a heteroaromatic secondary alcohol (1-(2furyl)ethanol).…”

“…The DKR of phenylglycine methyl ester (54) is shown in Scheme 21. The enantioselective ammonolysis was catalyzed by Candida antarctica lipase B for the preparation of (R)-phenylglycine (55). (R)-phenylglycine and its 4-hydroxy derivatives are key intermediates in the manufacture of penicillin and cephalosporin antibiotics.…”

“…The racemising catalyst was 1 mM benzaldehyde or 0.6 mM chloropyridoxal. Through this method, 80% of substrate conversion with an enantiomeric excess of 95% of (R)-phenylglycine (55) were achieved at 208C after 7 h reaction.…”

Asymmetric Transformations by Coupled Enzyme and Metal Catalysis: Dynamic Kinetic Resolution

“…Hulshof et al introduced 10 as an alcohol racemization catalyst [31] . Alcohol DKR was performed with 0.1 mol% of 10 , CALB, isopropyl butyrate as the acyl donor, potassium carbonate and about 20 mol% of the corresponding ketone at 70 ° C (Scheme 1.23 ).…”