123535-85-3Relevant articles and documents
Polymer-supported ferrocenyl oxazolines for the catalyzed highly enantioselective phenyl transfer to aldehydes
Bolm, Carsten,Hermanns, Nina,Cla?en, Arno,Muiz, Kilian
, p. 1795 - 1798 (2002)
A new chiral MeO-PEG-supported ferrocenyl oxazoline was synthesized and successfully employed in the enantioselective phenyl transfer to aldehydes. The products were obtained in high yields and with excellent enantioselectivities (up to 97% ee). Furthermo
Synthesis of novel 1,1′-bis(oxazolinyl)metallocenes and their application in the asymmetric phenyl transfer from organozincs to aldehydes
Bolm,Hermanns,Kesselgruber,Hildebrand
, p. 157 - 161 (2001)
Two novel C2-symmetric 1,1′-bis(oxazolinyl)metallocenes bearing two catalytic sites each have been employed in the asymmetric phenyl transfer from organozincs to aldehydes. Both, ferrocene (3) and ruthenocene (10) give very good yields and high
Boronic acids as versatile aryl sources for the highly enantioselective synthesis of chiral diarylmethanols on multigram scale
Rudolph, Jens,Schmidt, Frank,Bolm, Garsten
, p. 840 - 842 (2005)
Chiral diarylmethanols have been synthesized on gram scale in high yields with excellent enantioselectivities using a catalyst with a ferrocenyl oxazoline-based N,O-ligand and mixtures of diethylzinc and arylboronic acid as an aryl source.
The MPEG effect: Improving asymmetric processes by simple additives
Rudolph, Jens,Hermanns, Nina,Bolm, Carsten
, p. 3997 - 4000 (2004)
Small amounts of simple methoxy poly(ethylene glycol)s (MPEGs) have a beneficial effect on catalyzed asymmetric aryl and alkyl transfer reactions onto aldehydes. The enantiomeric excesses of the products are improved, and this MPEG effect allows a reduction of the catalyst loading by a factor of 10.
Tropos amino alcohol mediated enantioselective aryl transfer reactions to aromatic aldehydes
Pisani, Laura,Bochicchio, Carmela,Superchi, Stefano,Scafato, Patrizia
, p. 5939 - 5945 (2014)
The preparation of new chiral amino alcohols that possess a flexible biphenylazepine moiety and can work as tropos catalysts, is presented. In these compounds, the sign of the induced axial chirality depends on the nature of stereogenic centers near the flexible fragment and can determine the stereochemical outcome in asymmetric reactions mediated by them. The efficiency of these new ligands has been explored in the asymmetric addition of arylzinc species prepared in situ to aromatic aldehydes. Among them, amino alcohol (1R,2S)-4 gave the best results and afforded optically active diarymethanols, which are precursors of well-known chiral drugs, in high yields and with enantioselectivity up to 96 %.
Nickel-Catalyzed Intermolecular Asymmetric Addition of Aryl Iodides across Aldehydes
Zhu, Ziqi,Xiao, Jieshuai,Li, Mingjie,Shi, Zhuangzhi
supporting information, (2022/02/25)
Enantioenriched alcohols comprise much of the framework of organic molecules. Here, we first report that chiral nickel complexes can catalyze the intermolecular enantioselective addition of aryl iodides across aldehydes to provide diverse optically active secondary alcohols using zinc metal as the reducing agent. This method shows a broad substrate scope under mild reaction conditions and precludes the traditional strategy through the pre-generation of organometallic reagents. Mechanistic studies indicate that an in situ formed arylnickel, instead of an arylzinc, adds efficiently to aldehydes, forming a new C?C bond and a chiral nickel alkoxide that may be turned over by zinc powder.
Bio-inspired asymmetric aldehyde arylations catalyzed by rhodium-cyclodextrin self-inclusion complexes
Asahi, Kaoru,Fujiwara, Shin-Ichi,Iwasaki, Takanori,Kambe, Nobuaki,Takahashi, Ryota,Tsuda, Susumu,Ueda, Ryoji,Yamauchi, Hiroki
supporting information, p. 801 - 807 (2022/02/03)
Transition-metal catalysts are powerful tools for carbon-carbon bond-forming reactions that are difficult to achieve using native enzymes. Enzymes that exhibit inherent selectivities and reactivities through host-guest interactions have inspired widesprea
Binaphthyl-prolinol chiral ligands: Design and their application in enantioselective arylation of aromatic aldehydes
Yao, Chao,Chen, Yaoqi,Sun, Ruize,Wang, Chao,Huang, Yue,Li, Lin,Li, Yue-Ming
supporting information, p. 3644 - 3655 (2021/05/04)
Binaphthyl-prolinol ligands were designed and applied in enantioselective arylation of aromatic aldehydes and sequential arylation-lactonization of methyl 2-formylbenzoate. Under optimized conditions, the reactions provided the desired diarylmethanols and 3-aryl phthalides in up to 96% yields with up to 99% ee and up to 89% yields with up to 99% ee, respectively. In particular, essentially optically pure 3-aryl phthalides (over 99% ee) were obtained in large quantities through recrystallization. This journal is
Electronic Effect-Guided Rational Design of Candida antarctica Lipase B for Kinetic Resolution Towards Diarylmethanols
Li, Dan-Yang,Lou, Yu-Jiao,Xu, Jian,Chen, Xiao-Yang,Lin, Xian-Fu,Wu, Qi
supporting information, p. 1867 - 1872 (2021/02/12)
Herein, we developed an electronic effect-guided rational design strategy to enhance the enantioselectivity of Candida antarctica lipase B (CALB) mutants towards bulky pyridyl(phenyl)methanols. Compared to W104A mutant previously reported with reversed S-stereoselectivity toward sec-alcohols, three mutants (W104C, W104S and W104T) displayed significant improvement of S-enantioselectivity in the kinetic resolution (KR) of various phenyl pyridyl methyl acetates due to the increased electronic effects between pyridyl and polar residues. The electronic effects were also observed when mutating other residues surrounding the stereospecificity pocket of CALB, such as T42A, S47A, A281S or A281C, and can be used to manipulate the stereoselectivity. A series of bulky pyridyl(phenyl) methanols, including S-(4-chlorophenyl)(pyridin-2-yl) methanol (S-CPMA), the intermediate of bepotastine, were obtained in good yields and ee values. (Figure presented.).
Molecular switch manipulating Prelog priority of an alcohol dehydrogenase toward bulky-bulky ketones
Xu, Guochao,Dai, Wei,Wang, Yue,Zhang, Lu,Sun, Zewen,Zhou, Jieyu,Ni, Ye
, (2019/12/27)
Structure-guided rational design revealed the molecular switch manipulating the Prelog and anti-Prelog priorities of an NADPH-dependent alcohol dehydrogenase toward prochiral ketones with bulky and similar substituents. Synergistic effects of unconserved residues at 214 and 237 in small and large substrate binding pockets were proven to be vital in governing the stereoselectivity. The ee values of E214Y/S237A and E214C/S237 G toward (4-chlorophenyl)-(pyridin-2-yl)-methanone were 99.3% (R) and 78.8% (S) respectively. Substrate specificity analysis revealed that similar patterns were also found with (4’-chlorophenyl)-phenylmethanone, (4’-bromophenyl)-phenylmethanone and (4’-nitrophenyl)-phenylmethanone. This study provides valuable evidence for understanding the molecular mechanism on enantioselective recognition of prochiral ketones by alcohol dehydrogenase.
