Biocompatible metal-assisted C–C cross-coupling combined with biocatalytic chiral reductions in a concurrent tandem cascade

Schaaf, Patricia; Bayer, Thomas; Koley, Moumita; Schnürch, Michael; Bornscheuer, Uwe T.; Rudroff, Florian; Mihovilovic, Marko D.

doi:10.1039/c8cc05304a

Cited by 29 publications

(17 citation statements)

References 29 publications

(42 reference statements)

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“…Preparative scale integrated reactions were also carried out to explore the nitrile substrate scope. Various functionalised aromatic nitriles with electron-donating or -withdrawing groups in the para- (17)(18)(19)(20)(21) or meta-position (22)(23)(24) were well tolerated affording amides in good to excellent yields using the CGA009 NHase (Fig. 3).…”

Section: Resultsmentioning

confidence: 99%

“…However, mutual inactivation and different operating conditions of chemoand biocatalysts present a major challenge for the development of integrated processes 17 . Despite this, the merger of transition metals (TM) and biocatalysts has led to some notable cascadetype processes, including the combination of stereoselective bioreduction with Pd or Ni catalysts 18,19 . The merger of halogenase enzymes with Pd catalysed cross-coupling has also been deployed for the construction of C−C bonds via a net C−H bond functionalisation process 20,21 .…”

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confidence: 99%

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Merging enzymes with chemocatalysis for amide bond synthesis

et al. 2022

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Amides are one of the most fundamental chemical bonds in nature. In addition to proteins and other metabolites, many valuable synthetic products comprise amide bonds. Despite this, there is a need for more sustainable amide synthesis. Herein, we report an integrated next generation multi-catalytic system, merging nitrile hydratase enzymes with a Cu-catalysed N-arylation reaction in a single reaction vessel, for the construction of ubiquitous amide bonds. This synergistic one-pot combination of chemo- and biocatalysis provides an amide bond disconnection to precursors, that are orthogonal to those in classical amide synthesis, obviating the need for protecting groups and delivering amides in a manner unachievable using existing catalytic regimes. Our integrated approach also affords broad scope, very high (molar) substrate loading, and has excellent functional group tolerance, telescoping routes to natural product derivatives, drug molecules, and challenging chiral amides under environmentally friendly conditions at scale.

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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

Merging enzymes with chemocatalysis for amide bond synthesis

et al. 2022

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“…Other examples are simultaneous tandem diene reactions of glyoxal (O=CH-CH=O) with two equivalents of a Wittig reagent (Ph 3 P=CMeCO 2 Et) to reach symmetrical 1,3-dienes (32,33). Sequential diene formation has also been reported in the sequential tandem formation of 1,3dienes from two different ylides (34), as well as C-C crosscoupling tandem cascades (35), tandem catalysis (36) and other synthetic reactions (37)(38)(39)(40). Some chemical structures with S-X bonds have proved useful in photocleavage.…”

Section: Commentarymentioning

confidence: 99%

Two‐step Two‐intermediate Photorelease Bolm‐McCulla Reaction: Dual Release of Nitrene and Atomic Oxygen Reactive Intermediates

Rashid

Baker

Greer

2021

Photochem & Photobiology

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This article is a highlight of the paper by Isor et al. in this issue of Photochemistry and Photobiology. It describes the photolysis of a dibenzothiophene sulfoximine (bearing Nphenyl imino and S-oxide groups) to produce two reactive intermediates in tandem. The sulfoximine undergoes a S-N and S-O photocleavage to release phenyl nitrene and atomic oxygen [O( 3 P)]. The phenyl nitrene dimerizes to azobenzene or is trapped by diethylamine to reach an azepine. From there, atomic oxygen arises in a secondary photolysis of dibenzothiophene sulfoxide. A computational analysis also reveals that the S-N bond is labile for initial nitrene release, with the secondary release of atomic oxygen by S-O cleavage. Whether future sulfoximine scaffolds can produce the reverse order release of O( 3 P) then nitrene, or release both simultaneously, is yet to be established. Nonetheless, molecules with dual-intermediate release, such as coupled photoaffinity labeling and cellular oxidation, are worth pursuing.

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“…The current trend towards more efficient chemical transformations promotes not only the use of catalysts, rather than using activated compounds, but also the reduction of work-up steps by combining two or more reactions into sequential or concurrent cascades [30][31][32][33][34][35]. Considering this trend, a two-step route to (S)-tembamide ((S)-4) starting from 4-anisaldehyde (1) was envisioned (see Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Multi-Catalytic Route for the Synthesis of (S)-Tembamide

et al. 2019

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Enantiopure β-amino alcohols constitute one of the most significant building blocks for the synthesis of active pharmaceutical ingredients. Despite the availability of a range of chiral β-amino alcohols from a chiral pool, there is a growing demand for new enantioselective synthetic routes to vicinal amino alcohols and their derivatives. In the present study, an asymmetric 2-step catalytic route that converts 4-anisaldehyde into a β-amino alcohol derivative, (S)-tembamide, with excellent enantiopurity (98% enantiomeric excess) has been developed. The recently published initial step consists in a concurrent biocatalytic cascade for the synthesis of (S)-4-methoxymandelonitrile benzoate. The O-benzoyl cyanohydrin is then converted to (S)-tembamide in a hydrogenation reaction catalyzed by Raney Ni. To achieve hydrogenation of the nitrile moiety with highest chemoselectivity and enantioretention, various parameters such as nature of the catalyst, reaction temperature and hydrogen pressure were studied. The reported strategy might be transferrable to the synthesis of other N-acyl-β-amino alcohols.

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Biocompatible metal-assisted C–C cross-coupling combined with biocatalytic chiral reductions in a concurrent tandem cascade

Abstract: We present a concurrent chemo/biocatalytic one pot reaction cascade by combining a metal (Pd/Cu) assisted Liebeskind–Srogl coupling with an enantioselective enzymatic reduction for the production of chiral amines and alcohols.

Cited by 29 publications

References 29 publications

Merging enzymes with chemocatalysis for amide bond synthesis

Merging enzymes with chemocatalysis for amide bond synthesis

Two‐step Two‐intermediate Photorelease Bolm‐McCulla Reaction: Dual Release of Nitrene and Atomic Oxygen Reactive Intermediates

Multi-Catalytic Route for the Synthesis of (S)-Tembamide

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