title: Biotinylated Rh(III) complexes in engineered streptavidin for accelerated asymmetric C-H activation.
abstract: Enzymes provide an exquisitely tailored chiral environment to foster high catalytic activities and selectivities, but their native structures are optimized for very specific biochemical transformations. Designing a protein to accommodate a non-native transition metal complex can broaden the scope of enzymatic transformations while raising the activity and selectivity of small-molecule catalysis. Here, we report the creation of a bifunctional artificial metalloenzyme in which a glutamic acid or aspartic acid residue engineered into streptavidin acts in concert with a docked biotinylated rhodium(III) complex to enable catalytic asymmetric carbon-hydrogen (C-H) activation. The coupling of benzamides and alkenes to access dihydroisoquinolones proceeds with up to nearly a 100-fold rate acceleration compared with the activity of the isolated rhodium complex and enantiomeric ratios as high as 93:7.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA.
authors.forename: Todd K
authors.initials: TK
authors.lastname: Hyster
authors.forename: Livia
authors.initials: L
authors.lastname: Knörr
authors.forename: Thomas R
authors.initials: TR
authors.lastname: Ward
authors.forename: Tomislav
authors.initials: T
authors.lastname: Rovis
mesh_terms: D000475:Alkenes / Q000737:chemistry; D001549:Benzamides / Q000737:chemistry*; D019921:Biotinylation; D002244:Carbon / Q000737:chemistry; D002384:Catalysis; D020134:Catalytic Domain; D056831:Coordination Complexes / Q000737:chemistry*; D004789:Enzyme Activation; D004798:Enzymes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D016297:Mutagenesis, Site-Directed; D015202:Protein Engineering; D012238:Rhodium / Q000737:chemistry*; D019809:Streptavidin / Q000737:chemistry* / Q000235:genetics; D013379:Substrate Specificity
chemical_list: D000475:Alkenes; D001549:Benzamides; D056831:Coordination Complexes; D004798:Enzymes; D002244:Carbon; D006859:Hydrogen; D019809:Streptavidin; D012238:Rhodium