132545-36-9Relevant articles and documents
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.
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
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