A Switchable Catalyst Duo for Acyl Transfer Proximity Catalysis and Regulation of Substrate Selectivity
Abir Goswami1, Sudhakar Gaikwad1, Michael Schmittel1
1Center of Micro and Nanochemistry and Engineering, Organische Chemie I, University of Siegen, Adolf-Reichwein Str. 2, 57068, Siegen, Germany.
Abstract:
Enzymes are encoded with a gamut of information to catalyze a highly selective transformation by selecting the proper reactants from an intricate mixture of constituents. Mimicking biological machinery, two switchable catalysts with differently sized cavities and allosteric control are conceived that allow complementary size-selective acyl transfer in an on/off manner by modulating the effective local concentration of the substrates. Selective activation of one of two catalysts in a mixture of reactants of similar reactivity enabled upregulation of the desired product.
Related Concept Videos
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:24Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
02:17Regioselectivity of Electrophilic Additions to Alkenes: Markovnikov's Rule
The hydrohalogenation of an unsymmetrical alkene can yield two haloalkane products, depending on which vinylic carbon takes up the halogen. However, one product usually predominates, where hydrogen adds to the vinylic carbon bearing the...
02:50Catalysis
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
02:05Prochirality