3391-10-4Relevant articles and documents
A new C2-symmetric chiral bisphosphine ligand containing a bioxazole backbone: Highly enantioselective hydrosilylation of ketones
Lee, Sang-Gi,Lim, Chung Woo,Song, Choong Eui,Kim
, p. 4027 - 4031 (1997)
C2-Symmetric (4S,4'S)-2,2'-bis(o-diphenylphosphinophenyl-4,4',5,5'-tetrahydro-4,4'-bi(1,3 -oxazole) (1, Phos-Biox) has been designed and synthesized as a chiral ligand for metal-catalyzed reactions. The Phos-Biox 1 was found to be an efficient
Efficient whole-cell biotransformation in a biphasic ionic liquid/water system
Pfruender, Holger,Amidjojo, Maya,Kragl, Udo,Weuster-Botz, Dirk
, p. 4529 - 4531 (2004)
Biocompatible ionic liquids act as a substrate reservoir and an in situ extracting agent in biotransformations with whole cells (see scheme). In the reduction of 4-chloroacetophenone to (R)-1-(4-chlorophenyl)ethanol, high product concentration (82 g Lsup
Stable electroenzymatic processes by catalyst separation
Hildebrand, Falk,Luetz, Stephan
, p. 4998 - 5001 (2009)
A study was conducted to demonstrate stable electroenzymatic processes by catalyst separation. The influence of amino acids on the mediator activity by cyclic was determined to investigate the interactions between the mediator and the amino acids. An in p
Discovery and Redesign of a Family VIII Carboxylesterase with High (S)-Selectivity toward Chiral sec-Alcohols
Park, Areum,Park, Seongsoon
, p. 2397 - 2402 (2022/02/17)
Highly enantioselective lipase has been widely utilized in the preparation of versatile enantiopure chiral sec-alcohols through kinetic or dynamic kinetic resolution. Lipase is intrinsically (R)-selective, and it is difficult to obtain (S)-selective lipase. Recent crystal structures of a family VIII carboxylesterase have revealed that the spatial array of its catalytic triad is the mirror image of that of lipase but with a catalytic triad that is distinct from lipase. We, therefore, hypothesized that the family VIII carboxylesterase may exhibit (S)-enantioselectivity toward sec-alcohols similar to (S)-selective serine protease, whose catalytic triad is also spatially arrayed as its mirror image. In this study, a homologous enzyme (carboxylesterase from Proteobacteria bacterium SG_bin9, PBE) of a known family VIII carboxylesterase (pdb code: 4IVK) was prepared, which showed not only moderate (S)-selectivity toward sec-alcohols such as 3-butyn-2-ol and 1-phenylethyl alcohol but also (R)-selectivity toward particular sec-alcohols among the substrates explored. Furthermore, the (S)-selectivity of PBE has been significantly improved by rational redesign based on molecular modeling. Molecular modeling identified a binding pocket composed of Ser381, Ala383, and Arg408 for the methyl substituent of (R)-1-phenylethyl acetate and suggested that larger residues may increase the enantioselectivity by interfering with the binding of the slow-reacting enantiomer. As predicted, substituting Ser381with larger residues (Phe, Tyr, and Trp) significantly improved the (S)-selectivity of PBE toward all sec-alcohols explored, even the substrates toward which the wild-type PBE exhibits (R)-selectivity. For instance, the enantioselectivity toward 3-butyn-2-ol and 1-phenylethyl alcohol was improved from E = 5.5 and 36.1 to E = 2001 and 882, respectively, by single mutagenesis (S381F).
PQXdpap: Helical Poly(quinoxaline-2,3-diyl)s Bearing 4-(Dipropylamino)pyridin-3-yl Pendants as Chirality-Switchable Nucleophilic Catalysts for the Kinetic Resolution of Secondary Alcohols
Murakami, Ryo,Suginome, Michinori,Yamamoto, Takeshi
supporting information, p. 8711 - 8716 (2021/11/24)
Helically chiral poly(quinoxaline-2,3-diyl)s bearing 4-(dipropylamino)pyridin-3-yl pendants at the 5-position of the quinoxaline ring (PQXdpap) exhibited high catalytic activities and moderate to high selectivities (up to s = 87) in the acylative kinetic resolution of secondary alcohols. The solvent-dependent helical chirality switching of PQXdpap between pure toluene and a 1:1 mixture of toluene and 1,1,2-trichloroethane enabled the preparation of either compound of a pair of enantiomerically pure alcohols (>99% ee) from a single catalyst.
Synthesis, characterization and catalytic performance in enantioselective reactions by mesoporous silica materials functionalized with chiral thiourea-amine ligand
G?k, Ya?ar,G?k, Halil Zeki
, p. 853 - 874 (2020/11/10)
Chiral heterogeneous catalysts have been synthesized by grafting of silyl derivatives of (1R, 2R)- or (1S, 2S)-1,2-diphenylethane-1,2-diamine on SBA-15 mesoporous support. The mesoporous material SBA-15 and so-prepared chiral heterogeneous catalysts were characterized by a combination of different techniques such as X-ray diffractometry (XRD), Fourier transform infrared (FT-IR), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FESEM), and Brunauer–Emmett–Teller (BET) surface area. Results showed that (1R, 2R)- and (1S, 2S)-1,2-diphenylethane-1,2-diamine were successively immobilized on SBA-15 mesoporous support. Chiral heterogeneous catalysts and their homogenous counterparts were tested in enantioselective transfer hydrogenation of aromatic ketones and enantioselective Michael addition of acetylacetone to β-nitroolefin derivatives. The catalysts demonstrated notably high catalytic conversions (up to 99%) with moderate enantiomeric excess (up to 30% ee) for the heterogeneous enantioselective transfer hydrogenation. The catalytic performances for enantioselective Michael reaction showed excellent activities (up to 99%) with poor enantioselectivities. Particularly, the chiral heterogeneous catalysts could be readily recycled for Michael reaction and reused in three consecutive catalytic experiments with no loss of catalytic efficacies.
