A Chemoenzymatic Approach to Enantiomerically Pure Amines Using Dynamic Kinetic Resolution: Application to the Synthesis of Norsertraline

Thalén, Lisa K.; Zhao, Dongbo; Sortais, Jean‐Baptiste; Paetzold, Jens; Hoben, Christine; Bäckvall, Jan‐Erling

doi:10.1002/chem.200802303

Cited by 144 publications

(88 citation statements)

References 58 publications

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“…The substrate scope of the DKR protocol above was extended to include a wide range of primary amines [89]. Functional groups tolerated include fluorine, bromine, nitrile, nitrate, and trifluoromethyl.…”

Section: Scheme 34mentioning

confidence: 99%

Shvo’s Catalyst in Hydrogen Transfer Reactions

Warner

Casey

Bäckvall

2011

Bifunctional Molecular Catalysis

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This chapter reviews the use of Shvo's catalyst in various hydrogen transfer reactions and also discusses the mechanism of the hydrogen transfer. The Shvo catalyst is very mild to use since no activation by base is required in the transfer hydrogenation of ketones or imines or in the transfer dehydrogenation of alcohols and amines. The Shvo catalyst has also been used as an efficient racemization catalyst for alcohols and amines. Many applications of the racemization reaction are found in the combination with enzymatic resolution leading to a dynamic kinetic resolution (DKR). In these dynamic resolutions, the yield based on the starting material can theoretically reach 100%. The mechanism of the hydrogen transfer from the Shvo catalyst to ketones (aldehydes) and imines as well as the dehydrogenation of alcohols and amines has been studied in detail over the past decade. It has been found that for ketones (aldehydes) and alcohols, there is a concerted transfer of the two hydrogens involved, whereas for typical amines and imines, there is a stepwise transfer of the two hydrogens. One important question is whether the substrate is coordinated to the metal or not in the hydrogen transfer step(s). The pathway involving coordination to activate the substrate is called the inner-sphere mechanism, whereas transfer of hydrogen without coordination is called the outer-sphere mechanism. These mechanistic proposals together with experimental and theoretical studies are discussed.

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Section: Scheme 34mentioning

confidence: 99%

Shvo’s Catalyst in Hydrogen Transfer Reactions

Warner

Casey

Bäckvall

2011

Bifunctional Molecular Catalysis

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“…Examples of efficient amine racemization performed in the mild conditions required for combination with an enzyme in a DKR process are rare. Most of the examples involve redox processes [34][35][36][37][38][39] and catalysts based on noble metals like Pd, Ru or Ir. The metal catalyzed racemization of chiral amines occurs via removal of the hydrogen atom from the stereogenic carbon generating a prochiral species with a planar geometry.…”

Section: Racemization and Dynamic Kinetic Resolution Of Aminesmentioning

confidence: 99%

Heterogeneous Catalysts for Racemization and Dynamic Kinetic Resolution of Amines and Secondary Alcohols

et al. 2010

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This paper gives an overview of the available heterogeneous catalysts for racemization of chirally stable secondary alcohols and amines, and of the combination of these catalysts with immobilized enzymes in dynamic kinetic resolution (DKR) for production of enantiopure esters or amides. For the one-pot DKR process, compatibility of enzyme and heterogeneous catalyst is a major issue, and in some cases the combination fails because of (mutual) deactivation. Heterogeneous catalysts of various types, such as zeolites or oxides effect alcohol racemization; they function either via acid catalysis and carbenium chemistry, or via a redox pathway via the ketone. Dynamic kinetic resolution of aliphatic alcohols using a heterogeneous catalyst in mild conditions is however an open challenge. Heterogeneous amine racemization catalysts invariably operate using a redox mechanism via the imine. In this case, the scope encompasses benzylic and aliphatic amines. The practicality of the approach is illustrated with the production of enantiopure N-acylated homoserine lactones, which are signalling compounds in microbial communities.

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“…In addition, highly active imine intermediates are likely to take part in several side reactions, which are more favored at elevated temperatures [9,10]. To date, a ruthenium complex Shvo analogue 3 coupled with CALB is the most practical method for DKR of aliphatic and benzylic primary amines at 90 °C [38][39][40].…”

Section: Dynamic Kinetic Resolution Of Aminesmentioning

confidence: 99%

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

Wang

Zhao

2016

Catalysts

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Abstract:The application of biocatalysts in the synthesis of fine chemicals and medicinal compounds has grown significantly in recent years. Particularly, there is a growing interest in the development of one-pot tandem catalytic systems combining the reactivity of a chemical catalyst with the selectivity engendered by the active site of an enzyme. Such tandem catalytic systems can achieve levels of chemo-, regio-, and stereo-selectivities that are unattainable with a small molecule catalyst. In addition, artificial metalloenzymes widen the range of reactivities and catalyzed reactions that are potentially employable. This review highlights some of the recent examples in the past three years that combined transition metal catalysis with enzymatic catalysis. This field is still in its infancy. However, with recent advances in protein engineering, catalyst synthesis, artificial metalloenzymes and supramolecular assembly, there is great potential to develop more sophisticated tandem chemoenzymatic processes for the synthesis of structurally complex chemicals.

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A Chemoenzymatic Approach to Enantiomerically Pure Amines Using Dynamic Kinetic Resolution: Application to the Synthesis of Norsertraline

Cited by 144 publications

References 58 publications

Shvo’s Catalyst in Hydrogen Transfer Reactions

Shvo’s Catalyst in Hydrogen Transfer Reactions

Heterogeneous Catalysts for Racemization and Dynamic Kinetic Resolution of Amines and Secondary Alcohols

Tandem Reactions Combining Biocatalysts and Chemical Catalysts for Asymmetric Synthesis

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