Cooperative Tandem Catalysis by an Organometallic Complex and a Metalloenzyme

Abstract

Although chemical and enzymatic catalysts have been combined, reactions in which an organometallic catalyst and a metalloenzyme work cooperatively to create products, which cannot be generated with either catalyst alone or in comparable yields by sequential reactions of the two catalysts, have not been reported. Such reactions are challenging to achieve, in part because the milieu in which these catalysts operate are typically different. Herein, two classes of catalysts are demonstrated to react cooperatively in the same system. Combination of a metathesis catalyst and a P450 enzyme lead to a dynamic equilibration of alkenes and a selective epoxidation of the cross-metathesis products. These results show the potential of combining the two classes of catalysts for synthetic transformations.

One-Pot Combination of Metal- and Bio-Catalysis in Water for the Synthesis of Chiral Molecules

“…Several types of metathesis transformations (RCM (ring-closing metathesis) and CM (cross-metathesis), among others) have been carried out in water by: (i) introducing modifications in the catalyst structure; (ii) using co-solvents; or (iii) employing surfactants [73][74][75]. Thus, in this section, we cover the fruitful combination of two different Ru-catalyzed metathesis protocols (RCM and CM) in aqueous media with several biocatalyzed organic reactions [76][77][78][79][80]. Although none of the discussed protocols permits the synthesis of enantiopure products, they constitute very important contributions in the field of chemoenzymatic cascade processes performed in aqueous media and are worth mention in this review.…”

“…Thus, the first work in this field was reported by Zhao, Hartwig and co-workers in 2014 by describing the combination of the ruthenium-catalyzed CM between 10-undecenoic acid and trans-3-hexene with the subsequent epoxidation of the in situgenerated 10-tridecenoic acid using P450 BM3 from Bacillus megaterium in a biphasic medium [78]. Prior to this study, the authors assessed that P450 BM3 (combined with a phosphite dehydrogenase regeneration system) reacted with more than five-fold preference for the epoxidation of 10-tridecenoic acid over 10-undecenoic acid.…”

“…Not only the Ru-catalyzed ring-closing metathesis (RCM) of different diallyl compounds, but also the Ru-catalyzed cross-metathesis (CM) of functionalized olefins has been productively assembled with different biotransformations [78][79][80]. Thus, the first work in this field was reported by Zhao, Hartwig and co-workers in 2014 by describing the combination of the ruthenium-catalyzed CM between 10-undecenoic acid and trans-3-hexene with the subsequent epoxidation of the in situ-generated 10-tridecenoic acid using P450 BM3 from Bacillus megaterium in a biphasic medium [78].…”

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

“…Recently, Zhao and coworkers successfully combined Ru-catalyzed olefin metathesis with a P450-monooxygenase catalyzed oxidation in a biphasic system for the synthesis of various epoxides [60]. Importantly, this work demonstrated the power of chemoenzymatic one-pot processes to achieve higher yields compared with the sequential two-step reactions.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…A c c e p t e d M a n u s c r i p t 30 More complex examples of cross metathesis reactions are depicted in Scheme 8. Tandem single reaction event cross metathesis and biocatalysis (P450 oxidation of the alkene to the epoxide) was accomplished in a biphasic system using mesityl group analogs of catalyst 4 [525]. A variety of alkenylphosphonates (e.g.…”