109459-08-7Relevant academic research and scientific papers
Controllable stereoinversion in DNA-catalyzed olefin cyclopropanationviacofactor modification
Cheng, Yu,Hao, Jingya,Jia, Guoqing,Li, Can,Lu, Shengmei,Miao, Wenhui
, p. 7918 - 7923 (2021)
The assembly of DNA with metal-complex cofactors can form promising biocatalysts for asymmetric reactions, although catalytic performance is typically limited by low enantioselectivities and stereo-control remains a challenge. Here, we engineer G-quadruplex-based DNA biocatalysts for an asymmetric cyclopropanation reaction, achieving enantiomeric excess (eetrans) values of up to +91% with controllable stereoinversion, where the enantioselectivity switches to ?72% eetransthrough modification of the Fe-porphyrin cofactor. Complementary circular dichroism, nuclear magnetic resonance, and fluorescence titration experiments show that the porphyrin ligand of the cofactor participates in the regulation of the catalytic enantioselectivityviaa synergetic effect with DNA residues at the active site. These findings underline the important role of cofactor modification in DNA catalysis and thus pave the way for the rational engineering of DNA-based biocatalysts.
Dirhodium(II)tetrakis[3(S)-phthalimido-2-piperidinonate]: A novel dirhodium(II) carboxamidate catalyst for asymmetric cyclopropanation
Watanabe, Nobuhide,Matsuda, Hideo,Kuribayashi, Harumi,Hashimoto, Shun-Ichi
, p. 537 - 542 (2007/10/03)
Dirhodium(II) tetrakis[3(S)-phthalimido-2-piperidinonate] catalyzes cyclopropanation of α-methylstyrene with d-menthyl diazoacetate to give d-menthyl (1S,2S)-2-methyl-2-phenylcyclopropanecarboxylate of 90% de.
CHIRAL RHODIUM(II) CARBOXAMIDES. A NEW CLASS OF CATALYSTS FOR ENANTIOSELECTIVE CYCLOPROPANATION REACTIONS
Doyle, Michael P.,Brandes, Bridget D.,Kazala, Amy P.,Pieters, Roland J.,Jarstfer, Michael B.,et al.
, p. 6613 - 6616 (2007/10/02)
Chiral Rh2L4 (L = 4-substituted-oxazolidinones and methyl 2-pyrrolidone-5-carboxylate) having two nitrogen-rhodium bonds in the cis geometry at each rhodium face are effective catalysts for enantioselective intermolecular cyclopropanation reactions.
ENHANCEMENT OF STEREOSELECTIVITY IN CATALYTIC CYCLOPROPANATION REACTIONS
Doyle, Michael P.,Loh, Kuo-Liang,DeVries, Keith M.,Chinn, Mitchell S.
, p. 833 - 836 (2007/10/02)
Significat enhancement of trans(anti) stereoselectivity is achieved in rhodium(II) acetamide catalyzed cyclopropanation reactions of 2,3,4-trimethyl-3-pentyl diazoacetate (ODA) and diazoacetamides.
