Olefin metathesis catalysts embedded in β-barrel proteins: creating artificial metalloproteins for olefin metathesis

Abstract

This review summarizes the recent progress of Grubbs–Hoveyda (GH) type olefin metathesis catalysts incorporated into the robust fold of β-barrel proteins. Anchoring strategies are discussed and challenges and opportunities in this emerging field are shown from simple small-molecule transformations over ring-opening metathesis polymerizations to in vivo olefin metathesis.

Artificial Metalloenzymes: Challenges and Opportunities

“…Since these initial reports, olefin metathesis has served as a propitious playground for testing novel concepts in ArMs and was recently reviewed. 73,74…”

“…Since these initial reports, olefin metathesis has served as a propitious playground for testing novel concepts in ArMs and was recently reviewed. 73,74 The M75L-H76L-Q96C-M148L-H158L mutant of nitrobindin (NB4), a dimeric 10-stranded β-barrel protein, was used by the Hayashi, Okuda, and Schwaneberg groups to create a metathase by covalent anchoring via a maleimide-cysteine coupling. Initially, the conjugation of a cofactor with three different linker lengths 42−44 was attempted with only the longest linker 44 showing a modest coupling yield (25%) to NB4 (44•NB4) via an engineered cysteine Q96C, Scheme 20.…”

A study on selective transformation of norbornadiene into fluorinated cyclopentane-fused isoxazolines

“…The efficient catalytic activity and remarkable functional group tolerance of commercially available versatile Ru-based olefin metathesis catalysts have allowed wide applica-bility of these transformations [1][2][3][4][5][6][7][8]. Moreover, the robustness of many commercial Ru-based catalysts has enabled the general application of olefin metathesis in the synthesis of versatile functionalized heterocycles [9][10][11], a wide variety of natural products (especially macrocycles) [12], alkaloids [13], amino acids and functionalized biomolecules such as peptides [14][15][16][17][18][19][20] or various drugs [21]. Due to the ring strain, bicyclic systems and derivatives, such as norbornadiene derivatives can easily be converted across ROM or ROCM into a variety of alkenylated, functionalized scaffolds [22][23][24][25][26][27][28][29][30][31][32][33][34].…”

A Combined Bio-Chemical Synthesis Route for 1-Octene Sheds Light on Rhamnolipid Structure

“…Commonly, cell or media components inhibit metal catalysis [42,43,45]. Overcoming these challenges involves the utilization of compartmentalization strategies [42,46], utilization of biphasic systems, [47] generation of artificial metalloproteins capable of catalyzing the olefin metathesis reaction [48][49][50][51][52] or, if the enzyme allows, the utilization of cosolvents [53][54][55]. Ethenolysis utilizes ethylene as reaction partner and converts internal double bonds into terminal double bonds.…”