132545-36-9Relevant academic research and scientific papers
Engineering Dirhodium Artificial Metalloenzymes for Diazo Coupling Cascade Reactions**
Bultman, Max J.,Huang, Rui,Lewis, Jared C.,Li, Ying,Roux, Benoit,Upp, David M.
, p. 23672 - 23677 (2021/08/23)
Artificial metalloenzymes (ArMs) are commonly used to control the stereoselectivity of catalytic reactions, but controlling chemoselectivity remains challenging. In this study, we engineer a dirhodium ArM to catalyze diazo cross-coupling to form an alkene that, in a one-pot cascade reaction, is reduced to an alkane with high enantioselectivity (typically >99 % ee) by an alkene reductase. The numerous protein and small molecule components required for the cascade reaction had minimal effect on ArM catalysis. Directed evolution of the ArM led to improved yields and E/Z selectivities for a variety of substrates, which translated to cascade reaction yields. MD simulations of ArM variants were used to understand the structural role of the cofactor on ArM conformational dynamics. These results highlight the ability of ArMs to control both catalyst stereoselectivity and chemoselectivity to enable reactions in complex media that would otherwise lead to undesired side reactions.
Diastereo- and Enantioselective Synthesis of Fluorine Motifs with Two Contiguous Stereogenic Centers
Ponra, Sudipta,Rabten, Wangchuk,Yang, Jianping,Wu, Haibo,Kerdphon, Sutthichat,Andersson, Pher G.
, p. 13878 - 13883 (2018/10/24)
The synthesis of chiral fluorine containing motifs, in particular, chiral fluorine molecules with two contiguous stereogenic centers, has attracted much interest in research due to the limited number of methods available for their preparation. Herein, we report an atom-economical and highly stereoselective synthesis of chiral fluorine molecules with two contiguous stereogenic centers via azabicyclo iridium-oxazoline-phosphine-catalyzed hydrogenation of readily available vinyl fluorides. Various aromatic, aliphatic, and heterocyclic systems with a variety of functional groups were found to be compatible with the reaction and provide the highly desirable product as single diastereomers with excellent enantioselectivities.
Enantioselective β-Protonation by a Cooperative Catalysis Strategy
Wang, Michael H.,Cohen, Daniel T.,Schwamb, C. Benjamin,Mishra, Rama K.,Scheidt, Karl A.
, p. 5891 - 5894 (2015/05/27)
An enantioselective N-heterocyclic carbene (NHC)-catalyzed β-protonation through the orchestration of three distinct organocatalysts has been developed. This cooperative catalyst system enhances both yield and selectivity, compared to only the NHC-catalyz
Electrochemical carboxylation of cinnamate esters in MeCN
Wang, Huan,Zhang, Kai,Liu, Ying-Zi,Lin, Mei-Yu,Lu, Jia-Xing
, p. 314 - 318 (2008/09/16)
Electrochemical carboxylation of cinnamate esters has been carried out by cathodic reduction of C{double bond, long}C bond in an undivided cell equipped with Mg sacrificial anode and using MeCN saturated with CO2 as solvent. The yields and the
Highly Specific Fragmentation Processes of Isomeric Mixed Esters of Phenylsuccinic Acid Under Electron Impact
Vidavsky, I.,Mandelbaum, A.,Tamiri, T.,Zitrin, S.
, p. 287 - 292 (2007/10/02)
Isomeric mixed dialkyl phenylsuccinates, PhCH(COOR)CH2COOR', undergo a highly specific elimination of ROH under electron impact.A deuterium-labelling study showed that the hydrogen atom from the benzylic position 2 is abstracted in this process.These resu
